JP2015152808A - Liquid crystal alignment adjuvant and liquid crystal display element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal alignment adjuvant having the effect of completely dissolving or sufficiently suppressing defects generated in a liquid crystal composition drop fill (ODF:One Drop Fill) step being one of manufacturing steps of a liquid crystal display element, namely, dropping marks, and to provide a liquid crystal display element of a TN, IPS, FFS, VA, PSA, or PSVA, etc., type using the liquid crystal alignment adjuvant, excellent in display quality, hardly generating display defect, such as a seizure and having a high yield.SOLUTION: There is provided a liquid crystal alignment adjuvant having an effect of completely dissolving or sufficiently suppressing defects generated in a liquid crystal composition drop fill (ODF:One Drop Fill) step being one of manufacturing steps of a liquid crystal display element, namely, drop marks, and further provided a liquid crystal display element of a TN, IPS, FFS, VA, PSA, or PSVA, etc., type using the liquid crystal alignment adjuvant, excellent in display quality, hardly generating display defects, such as a seizure and having a high yield.

Description

  The present invention relates to a liquid crystal alignment aid for solving defects generated in a drop injection (ODF: One Drop Fill) step of a liquid crystal composition, which is one of the manufacturing steps of a liquid crystal display element, that is, a liquid crystal alignment aid and The present invention relates to the liquid crystal display element used.

  In a liquid crystal display element, a small amount of impurities contained in various materials constituting the liquid crystal display element such as an alignment film, a sealant, a color filter (CF) or a liquid crystal (liquid crystal composition) cause a chromatographic phenomenon on the surface of the alignment film. It is believed that causing the display and adsorbing with a biased distribution causes display defects.

  In order to suppress display defects, a method of preventing impurities from adsorbing to the alignment film surface by using a liquid crystal composition containing only liquid crystal molecules having an alkenyl skeleton in the terminal group (see Patent Document 1) is disclosed. ing. However, in this method, when improving liquid crystal physical properties such as response speed and viscosity or developing a new liquid crystal for a liquid crystal display element, the molecular structure that can be used is limited to those having an alkenyl skeleton at the end, and Liquid crystal molecules having an alkenyl skeleton have a problem in that the reliability or life of the liquid crystal display element is adversely affected.

  Also disclosed is a method of adding an amine, ether, benzene, toluene, xylene, chloroform, silicon oil or aliphatic hydrocarbon to the liquid crystal composition to increase the injection rate of liquid crystal and reduce adsorption (see Patent Document 2). Has been. However, this method has an effect of reducing display defects, but has a problem that display defects cannot be solved completely.

  Furthermore, a method of preventing the adsorption of impurities by deactivating the alignment film surface activated by rubbing by heat treatment (see Patent Document 3) is also disclosed. However, this method has a problem that it is not effective for a display element using an alignment film for VA that does not require rubbing.

  On the other hand, in a ferroelectric liquid crystal display element, a method of controlling alignment defects due to a chevron structure derived from a layer structure peculiar to a ferroelectric liquid crystal by applying a liquid crystal composition to the surface of an alignment film is disclosed (see Patent Document 4). ing. This method has the function of modulating the SmA-SmC * phase transition temperature of the liquid crystal phase at the interface where the liquid crystal composition applied to the alignment film surface contacts the ferroelectric liquid crystal and the applied liquid crystal composition. This is to control alignment defects due to the chevron structure. However, in the case of nematic liquid crystal, since it does not have a layer structure like ferroelectric liquid crystal, it is technically important to apply a liquid crystal composition having an effect of modulating the SmA-SmC * phase transition temperature to the alignment film surface. I don't have it. Further, when a highly polar liquid crystal compound is applied to the alignment film as described in the document, display defects of the nematic liquid crystal display element due to the chromatographic phenomenon of impurities on the alignment film surface cannot be prevented.

JP-A-9-59626 JP-A-9-26582 JP 2001-305545 A JP 2003-98553 A

  An object of the present invention is to completely eliminate or sufficiently suppress defects generated in a liquid crystal composition drop injection (ODF: One Drop Fill) process, that is, one of liquid crystal display element manufacturing processes. The object is to provide a liquid crystal alignment aid having the effect of Furthermore, to provide a liquid crystal display element such as a TN type, an IPS type, an FFS type, a VA type, a PSA type, or a PSVA type that has excellent display quality and is unlikely to cause display defects such as image sticking. is there.

  As a result of studying various compounds and various chemical substances, the present inventor applied a specific compound to the surface of the alignment film of the liquid crystal display element, thereby producing a liquid crystal composition which is one of the manufacturing processes of the liquid crystal display element. It has been found that there is an effect of completely eliminating or sufficiently suppressing defects that occur in the dropping drop (ODF) step, that is, dropping marks, and the present invention has been completed.

  That is, it has an effect of completely eliminating or sufficiently suppressing defects that occur in a liquid crystal composition drop injection (ODF: One Drop Fill) process, which is one of the liquid crystal display element manufacturing processes, that is, a drop mark. A liquid crystal alignment aid is provided, and further, a liquid crystal display such as a TN type, an IPS type, an FFS type, a VA type, a PSA type, or a PSVA type, which has excellent display quality and hardly causes display defects such as image sticking. Provide elements with high yield.

  TECHNICAL FIELD The present invention relates to a liquid crystal alignment aid, which completely eliminates drip marks generated in a drop injection (ODF: One Drop Fill) process, which is one of the manufacturing processes of a liquid crystal display element, or is sufficient. Therefore, it is very useful for improving the quality of liquid crystal display elements and improving production efficiency.

  The present invention relates to a liquid crystal alignment aid applied to a liquid crystal alignment film, and the liquid crystal alignment aid of the present application is represented by the general formula (I)

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms. represents a 10 alkenyloxy group having from one -CH 2 present in the radical _- or non-adjacent two or more -CH 2 _- may be replaced each independently -O- or -S- In addition, one or two or more hydrogen atoms present in the group may be each independently substituted with a fluorine atom or a chlorine atom, and ring A, ring B, and ring C are each independently , Trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4 A phenylene group, 2,3-difluoro-1, -Phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- 2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a hydrogen atom in the group may be substituted with a fluorine atom, Z ¹ and Z ² are , Each independently, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, -CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, _{-CH 2 CH 2 -COO -, -} CH 2 CH _2— OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CY ¹ = CY ² — (where Y ¹ and Y ² are , Each independently represents a fluorine atom or a hydrogen atom), represents —C≡C— or a single bond, n represents 0, 1 or 2). contains.

In general formula (I), R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or carbon. represents an alkenyloxy group having the number of atoms of 2 to 10, one -CH present in group ₂ - or non-adjacent two or more -CH ₂ - are each independently -O- or -S- It may be substituted, and one or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom. More specifically, at least one of R ¹ and R ² is an alkyl group having 3 to 7 carbon atoms, an alkoxyl group having 3 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 carbon atoms. It is preferably an alkenyloxy group having 7 carbon atoms, more preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms. Further, when importance is attached to the reliability or lifetime of the liquid crystal display element, R ¹ and R ² are preferably alkyl groups having 1 to 10 carbon atoms, and are preferably alkyl groups having 2 to 7 carbon atoms. Further preferred. When it is desired to improve the effect of eliminating dripping marks, at least one of R ¹ and R ² is preferably an alkyl group having 3 to 10 carbon atoms, and is an alkyl group having 4 to 10 carbon atoms. Is preferable, and an alkyl group having 5 to 10 carbon atoms is preferable. On the contrary, when the reliability or lifetime of the liquid crystal display element does not need to be regarded as important, at least one of R ¹ and R ² is preferably an alkenyl group having 2 to 10 carbon atoms, More preferably, it is an alkenyl group having 7 to 7 carbon atoms, more preferably an alkenyl group having 3 to 7 carbon atoms, further preferably an alkenyl group having 4 to 7 carbon atoms, and 5 to 7 carbon atoms. More preferably, it is an alkenyl group, both R ¹ and R ² are preferably alkenyl groups having 2 to 10 carbon atoms, more preferably alkenyl groups having 2 to 7 carbon atoms, More preferably, it is an alkenyl group having 3 to 7 carbon atoms, more preferably an alkenyl group having 4 to 7 carbon atoms, and an alkenyl group having 5 to 7 carbon atoms. More preferably it is.

  In general formula (I), ring A, ring B and ring C are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, or 2-fluoro-1,4-phenylene group. 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4 -Bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydro Represents a naphthalene-2,6-diyl group, the hydrogen atom in the group may be substituted with a fluorine atom, trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro- 1,4-phenylene group, 3-fluoro Oro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene group is preferred. More specifically, when the cell thickness of the liquid crystal display element is relatively thin, at least one of the ring A, the ring B, and the ring C is a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group. , A 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group or a 2,3-difluoro-1,4-phenylene group, preferably a 1,4-phenylene group More preferably, at least two are 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group Alternatively, a 2,3-difluoro-1,4-phenylene group is preferable, and a 1,4-phenylene group is more preferable. When the cell thickness of the liquid crystal display element is relatively large, at least one of ring A, ring B, and ring C is preferably a trans-1,4-cyclohexylene group, and at least two are trans- More preferably, it is a 1,4-cyclohexylene group.

In general formula (I), Z ¹ and Z ² are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, — CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH _{2 CH 2 -, - OCO-CH} 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO —, —CH ₂ —OCO—, —CY ¹ ═CY ² — (wherein Y ¹ and Y ² each independently represents a fluorine atom or a hydrogen atom), —C≡C— or a single bond represents _{a, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CF 2 _{-, - OCF 2 -, -} CH 2 CH 2 -, - CF 2 CF 2 - or a single bond are _{preferred, -OCH 2 -, - CH 2} O -, - CF 2 O -, - OCF 2 -, - CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond is more preferable, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — or a single bond is more preferable, and a single bond is particularly preferable. .

  In general formula (I), n represents 0, 1 or 2, preferably 0 or 1, and more preferably 0.

The compound represented by general formula (I) is preferably a compound represented by general formula (IA) to general formula (IF), and from general formula (IA) to general formula (I). More preferably, it is a compound represented by -C). In addition, although R < ¹ > and R < ² > in a formula is as above-mentioned, the hydrogen atom of the 1, 4- phenylene group in a formula may be substituted by the fluorine atom.

  The general formula (IA) is preferably from the formula (I-Aa) to the formula (IA-Ae).

  The general formula (IB) is preferably the formula (I-Ba) to the formula (I-Be).

  The general formula (IC) is preferably from the formula (I-Ca) to the formula (I-Ce).

  The general formula (IA) is preferably from the formula (I-Af) to the formula (I-An).

The liquid crystal alignment aid of the present invention may contain only the compound represented by formula (I) as an ingredient, but as an additive, an antioxidant, a light stabilizer (HALS), an ultraviolet absorber, an infrared absorber or a polymerization agent. May contain a functional compound.
The liquid crystal alignment aid of the present invention preferably contains, for example, a hindered phenol represented by general formula (H-1) to general formula (H-4) as an antioxidant.

In general formula (H-1) to general formula (H-4), R ^H1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or It represents an alkenyloxy group having 2 to 10 carbon atoms, one -CH ₂ present in the radical - or non-adjacent two or more -CH ₂ - are each independently -O- or -S- In addition, 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 an alkyl group having 2 to 7 carbon atoms, an alkoxyl 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. An alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable.

In general formula (H-1) to general formula (H-4), ^MH4 is an alkylene group having 1 to 15 carbon atoms (one or more —CH ₂ — in the alkylene group is an oxygen atom) as but not immediately adjacent, -O -, - CO -, - COO -, - OCO- may be substituted _{in), -. 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 with a fluorine atom) or trans- Represents a 1,4-cyclohexylene group, but is an alkylene group having 1 to 14 carbon atoms In view of volatility, a large number of carbon atoms is preferable. However, in consideration of viscosity, it is preferable that the number of carbon atoms is not too large. Therefore, M in the general formula (II) according to the present invention is carbon. 2 to 12 atoms are more preferred, 3 to 10 carbon atoms are more preferred, 4 to 10 carbon atoms are more preferred, 5 to 10 carbon atoms are more preferred, and 6 to 10 carbon atoms are still more preferred.

  In general formula (H-1) to general formula (H-4), one or more non-adjacent —CH═ in the 1,4-phenylene group may be substituted by —N═. Further, each hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.

In general formula (H-1) to general formula (H-4), one or two or more non-adjacent —CH ₂ — in the 1,4-cyclohexylene group is replaced by —O— or —S—. May be. In addition, each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.

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

  The liquid crystal alignment aid of the present invention preferably contains formula (H-11), formula (H-12), or formula (H-14).

The liquid crystal alignment aid of the present invention may contain 1 ppm by mass or more of the above-mentioned additives, preferably 10 ppm by mass or more, preferably 20 ppm by mass or more, and more preferably 50 ppm by mass or more. The upper limit of the third component is 10,000 ppm by mass, preferably 1000 ppm by mass, preferably 500 ppm by mass, and preferably 100 ppm by mass.
The dielectric anisotropy (Δε) of the liquid crystal composition dropped into the liquid crystal display element (ODF: One Drop Fill) may be negative or positive.
The liquid crystal composition preferably contains one or more compounds represented by the following general formula (LC).

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one or more CH ₂ groups in the group are oxygen atoms. May be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— such that one or more in the group The hydrogen atom of may be optionally substituted with a halogen atom,
A ^LC1 and A ^LC2 are each independently
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom), and (c) 1 , 4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl A group or a group selected from the group consisting of a chroman-2,6-diyl group, but one or more hydrogen atoms contained in the group (a), group (b) or group (c) Each independently may be substituted with F, Cl, CF ₃ or OCF ₃ ,
Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, Represents —OCF ₂ —, —CF ₂ O—, —COO— or —OCO—,
Y ^LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one or more CH in the group _{The two} groups are —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF ₂ so that oxygen atoms are not directly adjacent to _{each other.} -One or more hydrogen atoms in the group may be optionally substituted with a halogen atom,
a represents an integer of 1 to 4, but a represents 2, 3 or 4, and when there are a plurality of ^ALC1 , the plurality of ^ALC1 may be the same or different, and ^ZLC is When there are a plurality of Z ^LCs , the plurality of Z ^LCs may be the same or different. )
When the dielectric anisotropy (Δε) of the liquid crystal composition is negative, the liquid crystal composition preferably contains a compound having a negative dielectric anisotropy (Δε) and an absolute value larger than 3. It is more preferable that the liquid crystal composition contains a compound having a negative dielectric anisotropy (Δε) and an absolute value larger than 4, and a negative dielectric anisotropy (Δε) and an absolute value of 5 More preferably, the liquid crystal composition contains a larger compound.

  As the compound represented by the general formula (LC), the compound having a negative dielectric anisotropy (Δε) and an absolute value larger than 3 is preferably a compound represented by the general formula (II), The total proportion of these in the liquid crystal composition is 20% or more, preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.

In general formula (II), R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon atom. represents the number 2 10 alkenyloxy group, ^{R 1} and ^R present in the ² one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O- and / Alternatively, -S- may be substituted, and one or more hydrogen atoms present in R ¹ and R ² may be independently substituted with a fluorine atom or a chlorine atom. R ¹ and R ² in the formula are each independently a linear alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom More preferably, it is an alkenyloxy group having 2 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ² is an alkoxyl group having 1 to 5 carbon atoms. It is particularly preferred that

  In general formula (II), ring A and ring B are each independently trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro. -1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2 2.2] Octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2, Represents a 6-diyl group. Ring A and ring B in the formula are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4. -Phenylene group, 3,5-difluoro-1,4-phenylene group or 2,3-difluoro-1,4-phenylene group is more preferable, and trans-1,4-cyclohexylene group or 1,4 A phenylene group is particularly preferred.

  In general formula (II), p represents 0, 1 or 2. More preferably, p in the formula is independently 0 or 1.

In the general formula (II), _{Z, -OCH 2 -, - CH 2} O -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond . Z in the _{formula, -CH 2 O -, - CF} 2 O -, - CH 2 CH 2 - or more preferably a single bond, particularly preferably _-CH 2 O-or a single bond.

  Although the said compound contains 1 type (s) or 2 or more types, it is preferable to contain 2 to 10 types.

  The compound represented by general formula (II) is preferably a compound represented by general formula (II-A1) to general formula (II-A5), and from general formula (II-B1) to general formula (II). -B5) is also preferred, and compounds of general formula (II-A1) to general formula (II-A5) are more preferred, and general formula (II-A1) or general formula (II) -A3) is particularly preferred.

In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one or two existing in R ³ and R ⁴ The above hydrogen atoms may be independently substituted with fluorine atoms.

  As a further component, the compound represented by the general formula (LC) preferably contains one or more compounds represented by the general formulas (V-1) and (V-2). The amount is preferably from 2 to 30% by weight, more preferably from 2 to 25% by weight, particularly preferably from 3 to 20% by weight.

In the formula, R ²¹ and R ²² are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Although an alkenyloxyl group is represented, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable.

  When the dielectric anisotropy (Δε) of the liquid crystal composition is positive, the liquid crystal composition preferably contains a compound having a positive dielectric anisotropy (Δε) and an absolute value larger than 3. It is more preferable that the liquid crystal composition contains a compound having a positive dielectric anisotropy (Δε) and an absolute value greater than 4. The liquid crystal composition preferably has a positive dielectric anisotropy (Δε) and an absolute value of 5 More preferably, the liquid crystal composition contains a larger compound.

  As a compound represented by the general formula (LC), a compound having a positive dielectric anisotropy (Δε) and an absolute value larger than 3 is a general formula (Na), a general formula (Nb) or a general formula (Pa The total ratio of these in the liquid crystal composition is 30% or more, preferably 40% or more, and more preferably 50% or more.

In the formula, R ^N1 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the group are each independent. May be substituted by -C≡C-, -O-, -CO-, -COO- or -OCO-, but may be an alkyl group having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms Groups are preferred.

Each ring A independently represents a 1,4-cyclohexylene group (one or two or more non-adjacent —CH ₂ — in the group may be substituted by —O— or —S—). ) Or a 1,4-phenylene group (one or two or more non-adjacent —CH═ in the group may be substituted by —N═), and each hydrogen atom in the group is independent. May be substituted with a cyano group, a fluorine atom or a chlorine atom, but a 1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, a 1,4-phenylene group, a 3-fluoro-1,4 A -phenylene group or a 3,5-difluoro-1,4-phenylene group is preferred.

Z ^{N1 and} Z ^N2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O. —, —COO—, —OCO— or —C≡C— is represented, but a single bond, —CH ₂ CH ₂ —, —CH ₂ O— or —CF ₂ O— is more preferable.

n ^N1 represents 0, 1, 2, 3 or 4, but when n ^N1 is 2, 3 or 4 and a plurality of rings A are present, they may be the same or different, and In addition, when there are a plurality of Z ^N1 , they may be the same or different.

X ^N1 , X ^N2 , X ^N3 , X ^N4 and X ^N5 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom.

Y ^N1 represents a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. A methyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group is preferred, and a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group is more preferred.

In the general formula (Pa), R ^Nc1 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and one or non-adjacent two or more —CH ₂ — in the group is Each independently may be substituted by —C≡C—, —O—, —CO—, —COO— or —OCO—, but may be an alkyl group having 1 to 5 carbon atoms or 2 to 2 carbon atoms. An alkenyl group of 5 is preferred.

In general formula (Pa), rings P ¹ , P ² and P ³ are each independently a 1,4-cyclohexylene group (one in the group or two or more non-adjacent —CH ₂ — is —O -Or -S- may be substituted) or a 1,4-phenylene group (one or non-adjacent two or more -CH = in the group may be substituted by -N =). ), And each hydrogen atom in the group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, but a 1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, 1 , 4-phenylene group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene group is preferred.

In the general formula (Pa), Z ^Nc1 , Z ^Nc2 or Z ^Nc3 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—. _{, -OCF 2 -, - CF 2} O -, - COO -, - OCO- or represents a -C≡C-, a single _{bond, -CH 2 CH 2 -, -} CH 2 O- or _-CF 2 O- Is more preferable, and it is more preferable that any one of Z ^Nc1 , Z ^{Nc2 and} Z ^Nc3 present is a single bond.
In the general formula (Pa), n ^c1 , n ^{c2, and} n ^c3 each independently represent 0, 1 or 2. n ^c1 + n ^c2 + n ^c3 represents 1 to 5, more preferably 4 or less, and particularly preferably 3 or less.

In the general formula (Pa), X ^Nc1 and X ^Nc2 each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom.

In formula (Pa), Y ^Nc1 represents a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. Is preferably a fluorine atom, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group, more preferably a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group.

  The compound represented by the general formula (Na) is preferably a compound selected from the group of compounds represented by the general formula (Na01) to the general formula (Na12).

In general formula (Na01) to general formula (Na12), R ^Na1 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and one or two or more non-adjacent groups in the group Each of —CH ₂ — may be independently substituted by —C≡C—, —O—, —CO—, —COO— or —OCO—, but may be an alkyl group having 1 to 5 carbon atoms. Alternatively, an alkenyl group having 2 to 5 carbon atoms is preferable.

In the general formula (Na01) to general formula (Na12), Z ^Na1 or Z ^Na2 each independently represents a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH. _{2 O -, - OCF 2 -} , - CF 2 O -, - COO -, - OCO- or represents a -C≡C-, a single _{bond, -CH 2 CH 2 -, -} CH 2 O- or -CF ₂ O- is more preferable.

In the general formulas general formula ^{(Na01) (Na12), X} Na5 from ^{X Na1,} each independently, represent a hydrogen atom, a chlorine atom or a fluorine atom.

In general formula (Na01) to general formula (Na12), ^YNa1 represents a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or 2,2,2- Represents a trifluoroethyl group, preferably a fluorine atom, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group, preferably a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group. Further preferred.

  The compound represented by General Formula (Nb) is preferably a compound selected from the group of compounds represented by General Formula (Nb1) to General Formula (Nb16).

In the general formula (Nb1) to general formula (Nb16), R ^Nb1 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and one in the group or two or more adjacent to each other Each of —CH ₂ — may be independently substituted by —C≡C—, —O—, —CO—, —COO— or —OCO—, but may be an alkyl group having 1 to 5 carbon atoms. Alternatively, an alkenyl group having 2 to 5 carbon atoms is preferable.

In the general formulas (Nb1) to (Nb16), X ^Nb1 to X ^Nb5 each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom.

In formulas (Nb1) to (Nb16), Y ^Nb1 represents a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or 2,2,2- Represents a trifluoroethyl group, preferably a fluorine atom, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group, preferably a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group. Further preferred.

  The compound represented by the general formula (Pa) is preferably a compound selected from the group of compounds represented by the general formula (P01) to the general formula (P80).

In the general formula (P01) to general formula (P80), R ^Nc1 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and one or two or more non-adjacent groups in the group Each of —CH ₂ — may be independently substituted by —C≡C—, —O—, —CO—, —COO— or —OCO—, but may be an alkyl group having 1 to 5 carbon atoms. Alternatively, an alkenyl group having 2 to 5 carbon atoms is preferable.

In formula (P01) to formula (P80), Y ^Nc2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or 2,2. , 2-trifluoroethyl group, preferably a fluorine atom, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group, and a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group. More preferably it is.

  Examples of the compound represented by the general formula (Pa) further include the following compounds.

  The dielectric anisotropy (Δε) of a liquid crystal composition dropped into a liquid crystal display element (ODF: One Drop Fill) is negative or positive. A compound having a property (Δε) of −1 to +1 (preferably a dielectric anisotropy (Δε) of −0.5 to +0.5) can be contained. Specifically, the compound represented by the general formula (LC) preferably contains one or more compounds represented by the general formula (L).

In the general formula (L), R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, Two or more adjacent —CH ₂ — may be independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. good.

In general formula (L), OL represents 0, 1, 2, or 3, and 0, 1, or 2 is preferable. When OL is 2 or 3, and a plurality of L ^L2 are present, they may be the same or different. When OL is 2 or 3, and a plurality of ^BL3 are present, they may be the same or different.

In the general formula (L), B ^L1 , B ^L2 and B ^L3 each independently represent a 1,4-cyclohexylene group (one —CH ₂ — present in this group or _two not adjacent to each other). more -CH ₂ -. may be replaced by -O-) or 1,4-phenylene group (the one -CH = or nonadjacent present in group two or more -CH = May be replaced by -N =, and one or two or more hydrogen atoms may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom.

In General Formula (L), L ^L1 and L ^L2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO. —, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C— are represented.

  Although it is preferable to contain 1 type, or 2 or more types of compounds represented by general formula (L), it is more preferable to contain 1 to 20 types, and it is more preferable to contain 2 to 10 types.

  The compound represented by General Formula (L) is preferably a compound selected from the group of compounds represented by General Formula (III-A) to General Formula (III-J).

In general formula (III-A) to general formula (III-J), R ⁵ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. To an alkyl group having 5 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable. R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, More preferably, it is an alkyl group having 1 to 5 carbon atoms, an alkoxyl 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.

  The compound represented by the general formula (L) includes the general formula (III-A), the general formula (III-D), the general formula (III-F), the general formula (III-G), and the general formula (III-H). It is more preferable that the compound is selected from general formula (III-A), general formula (III-F), general formula (III-G), and general formula (III-H). Is particularly preferred.

In the compounds represented by general formula (III-D), general formula (III-G), and general formula (III-H), R ⁵ represents an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. To an alkenyl group having 5 to 5 carbon atoms, R ⁶ is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. In the compound represented by the general formula (III-F), R ⁵ and R ⁶ are preferably each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

  The content of the compound represented by the general formula (L) is preferably 0% by mass to 80% by mass, more preferably 1% by mass to 60% by mass, and 3% by mass to 60% by mass. More preferably, it is more preferably 10% by mass to 60% by mass, further preferably 20% by mass to 60% by mass, and further preferably 30% by mass to 60% by mass.

  It is preferable that the liquid crystal composition that is dropped into the liquid crystal display element of the present invention (ODF: One Drop Fill) necessarily contains the general formula (III-A). Specifically, it is preferable to always contain the formula (III-Aa) or the formula (III-Ab).

  As a compound represented by general formula (L), you may contain 1 type, or 2 or more types of compounds represented by general formula (VIII-c) to general formula (VIII-e).

In general formula (VIII-c) to general formula (VIII-e), R ⁵¹ and R ⁵² are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, carbon An alkenyl group having 2 to 5 atoms and an alkenyloxy group having 2 to 5 carbon atoms are represented, and X ⁵¹ and X ⁵² each independently represent a fluorine atom, a chlorine atom or a hydrogen atom.

  More specifically, a compound of formula (V-6.1) can be mentioned.

  As a compound represented by general formula (L), you may contain 1 type, or 2 or more types of compounds represented by general formula (V-9.1) to general formula (V-9.3).

  The liquid crystal composition may contain 0.01 to 2% by mass of a polymerizable compound such as a biphenyl derivative or a terphenyl derivative as a polymerizable monomer. More specifically, the general formula (M)

You may contain the polymeric compound represented by these by 1 type, or 2 or more types.

In General Formula (M), X ²⁰¹ and X ²⁰² each independently represent a hydrogen atom, a methyl group, or a —CF ₃ group. X ²⁰¹ and X ²⁰² are each preferably a diacrylate derivative that is a hydrogen atom, and a dimethacrylate derivative that is both a methyl group, and a compound in which one is a hydrogen atom and the other is a methyl group. A preferred compound can be used depending on the application, but in the PSA display element, the polymerizable compound represented by the general formula (M) preferably has at least one methacrylate derivative, and preferably has two.

In General Formula (M), Sp ²⁰¹ and Sp ²⁰² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 7). And an oxygen atom is bonded to the ring. In the PSA mode liquid crystal display element, at least one of Sp ²⁰¹ and Sp ²⁰² is preferably a single bond, both of which are single bonds or one of which is a single bond and the other is an alkylene having 1 to 8 carbon atoms. It is preferably a group or —O— (CH ₂ ) _s —. In this case, an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.

In general formula (M), ring M ²⁰¹ , ring M ²⁰² and ring M ²⁰³ are each independently a trans-1,4-cyclohexylene group (one or non-adjacent two or more —CH in the group). ₂ -may be substituted by -O- or -S-), 1,4-phenylene group (one or two or more non-adjacent -CH = in the group is substituted by -N =. 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a hydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and each hydrogen atom in the group is independently a fluorine atom, a -CF ₃ group, An alkyl group having 1 to 10 carbon atoms, 1 carbon atom To 10 alkoxyl groups or formula (R-1) to formula (R-15).

In General Formula (M), Z ²⁰¹ and Z ²⁰² each independently represent —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, — CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH _{2 CH 2 -, - OCO-CH} 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO —, —CH ₂ —OCO—, —CY ¹ ═CY ² — (wherein Y ¹ and Y ² each independently represents a fluorine atom or a hydrogen atom), —C≡C— or a single bond -COO-, -OCO-, -CH = CH-COO-,- H = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO-, —CH ₂ CH ₂ —OCO—, —C≡C— or a single bond is preferable, —COO—, —OCO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH _{-, - OCO-CH = CH} -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or a single bond is more preferable.

In the general formula (M), n ²⁰¹ represents 0, 1 or 2, with 0 or 1 being preferred. However, when there are a plurality of rings M ²⁰² and Z ²⁰² , they may be different or the same.

  At least one type of polymerizable compound represented by formula (M) may be contained, preferably 1 to 5 types, more preferably 1 to 3 types.

  The content of the general formula (M) is preferably 0.01 to 2.00% by mass, more preferably 0.05 to 1.00% by mass, and 0.10 to 0.50% by mass. It is particularly preferred.

More specifically, when n ²⁰¹ is 0 in the general formula (M), the ring structure between Sp ²⁰¹ and Sp ²⁰² is preferably the formula (XXa-1) to the formula (XXa-5), The formula (XXa-1) to the formula (XXa-3) are more preferable, and the formula (XXa-1) or the formula (XXa-2) is particularly preferable. However, both ends of the equation shall be connected to Sp ²⁰¹ or Sp ²⁰² .

  The polymerizable compound represented by the general formula (M) containing these skeletons is suitable for a PSA mode liquid crystal display element because of its alignment regulating force after polymerization, and a good alignment state can be obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.

  From the above, as the polymerizable monomer, compounds represented by formula (XX-1) to general formula (XX-10) are preferable, and formula (XX-1) to formula (XX-4) are more preferable.

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

In formula (XX-1) to general formula (XX-10), the hydrogen atom in the 1,4-phenylene group is further —F, —Cl, —CF ₃ , —CH ₃ , or formula (R-1). To (R-15) may be substituted.

In the general formula (M), when n ²⁰¹ is 1, for example, a polymerizable compound such as the formula (M31) to the formula (M48) is preferable.

Hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formula (M48) from equation (M31) is _{further, -F, -Cl, -CF 3,} -CH 3, wherein the formula (R-1) It may be substituted by any of (R-15).

  The polymerizable compound represented by the general formula (M) containing these skeletons is suitable for a PSA mode liquid crystal display element because of its alignment regulating force after polymerization, and a good alignment state can be obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.

In the general formula (M), when n ²⁰¹ is 1 and there are a plurality of formulas (R-1) or (R-2), for example, polymerizable compounds such as formulas (M301) to (M316) preferable.

The hydrogen atoms in the 1,4-phenylene group and naphthalene group in the compounds represented by the general formulas (M301) to (M316) are further substituted with —F, —Cl, —CF ₃ , or —CH ₃ . May be.

  As the polymerizable compound represented by General Formula (M), for example, polymerizable compounds such as Formula (Ia-1) to Formula (Ia-31) are also preferable.

  It is preferable to polymerize the liquid crystal composition containing these polymerizable compounds in the present liquid crystal display element.

  The liquid crystal alignment aid of the present invention can be attached to the surface of the alignment film for liquid crystal by a method such as dipping, spin coating, spraying, vapor deposition, inkjet, slit coater or printing, but spraying, inkjet, slit coater or printing. Is preferred. It is also preferable to adjust the coating amount with an air cutter or the like.

  When adhering to the surface of the alignment film for liquid crystal, the liquid crystal alignment aid may be used as it is or may be dissolved in a solvent and used as a solution. However, it is preferably used as a solution depending on requirements such as viscosity. Moreover, it is also preferable to use it while heating in order to adjust the viscosity.

  When used as a solution, the concentration of the liquid crystal alignment aid in the solution is preferably 0.1% by mass or more, preferably from 0.1% by mass to 10% by mass, and from 0.2% by mass. It is more preferably 10% by mass, further preferably 0.5% by mass to 10% by mass, further preferably 0.5% by mass to 4% by mass, and 1% by mass to 4% by mass. More preferably it is.

  The solvent is preferably an organic solvent, and the organic solvent is preferably a hydrocarbon organic solvent as long as it has a solubility capable of dissolving 0.1% or more of the compound represented by the general formula (I). You may mix and use the hydrocarbon type organic solvent of a seed or more.

  Examples of such a solvent include toluene, xylene, cumene, benzene, ethylbenzene, hexane, cyclohexane, cyclohexene, cyclopentane, methylcyclopentane, 2-methylhexane, heptane, octane, nonane, decane, undecane, dodecane, Aromatic hydrocarbon solvents such as petroleum benzine, ligroin, petroleum ether, gasoline, kerosene and mesitylene, methyl acetate, ethyl acetate, propyl acetate, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, Ester solvents such as isoamyl propionate, isoamyl isobutyrate, ethylene carbonate and propylene carbonate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydro Ketone solvents such as cis-4-methyl-2-pentanone, diisobutylketone, cyclopentanone, ether solvents such as tetrahydrofuran (THF), 1,2-dimethoxyethane, diisopentyl ether, anisole, N, N- Amide solvents such as dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone, nitrile solvents such as acetonitrile, alcohol solvents such as methanol and isopropyl alcohol, dimethyl sulfoxide (DMSO), etc. Sulfoxide solvents, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethyl Glycols such as ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate Solvents, halogen solvents such as dichloromethane, chloroform, chlorobenzene and dichloroethane, lactone solvents such as γ-butyrolactone (GBL), lactam solvents such as N-methyl-2-pyrrolidinone (NMP) and γ-butyrolactam, etc. It is done. Among these, ethanol, methanol, isopropyl alcohol, acetone, toluene or hexane is preferable, and ethanol, isopropyl alcohol or hexane is more preferable. When there is a need for a high flash point, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), γ-butyrolactone (GBL), ethanol, methanol, isopropyl alcohol , Polar solvents such as acetone and benzene, toluene, ethylbenzene, xylene, hexane, cyclohexane, cyclohexene, cyclopentane, methylcyclopentane, 2-methylhexane, heptane, octane, nonane, dodecane, petroleum benzine, ligroin, petroleum ether, Mixing a hydrocarbon-based organic solvent such as gasoline or kerosene is preferable because it has lower flammability than using only a hydrocarbon-based organic solvent.

  The polarity of the hydrocarbon-based organic solvent is preferably a dielectric constant of 40 or less, more preferably 35 or less, further preferably 30 or less, further preferably 25 or less, and 20 or less. More preferably, it is more preferably 15 or less, further preferably 10 or less, further preferably 5 or less, and further preferably 3 or less. In addition, if the polarity of the solvent is low, there may be a problem in printing characteristics, so the polarity of the solvent constituting the liquid crystal alignment aid of the present invention preferably has an absolute value of relative dielectric constant at 25 ° C. of 10 or less. It is more preferably 5 or less, and further preferably 3 or less.

In the case of attaching a nonpolar organic compound by immersion, a method in which one side of the substrate is coated and nonpolar liquid crystal is attached and then peeled off is preferable. In this case, the immersion time is preferably within 30 minutes, preferably within 10 minutes. It is more preferable. As a method for removing the solvent after the immersion, there is a method by heat drying, vacuum drying or gas injection. Among them, after immersion, an inert gas such as nitrogen gas or argon gas is immediately blown off with an air knife or an air gun to remove the solvent, and preferably under reduced pressure of 1.3 × 10 ³ to 1.3 Pa. It is preferable to completely remove the solvent under a reduced pressure of 6.7 × 10 ² to 1.3 Pa.

  The liquid crystal alignment aid of the present invention may be applied to any of organic, inorganic or composite alignment films. Specifically, polyimide alignment films, polyimide LB films, cellulose alignment films, and alignment of silane coupling agents. Applicable to film, polyvinyl alcohol alignment film, polyamide alignment film, epoxy acrylate alignment film, silanol oligomer alignment film, polyacrylonitrile alignment film, phenol resin alignment film, polyoxazole alignment film, cyclized polyisoprene alignment film or SiO vapor deposition film In particular, it is preferably applied to a polyimide alignment film or a polyamide alignment film.

  The liquid crystal alignment aid of the present invention is effective in both the vertical direction and the horizontal direction as the direction in which the alignment film aligns the liquid crystal molecules, but it is particularly preferable to apply to the vertical alignment film. The alignment film may or may not be subjected to an alignment treatment by rubbing or photo-alignment.

  The nematic liquid crystal display element is preferably an active matrix liquid crystal display element, and can be applied to any of the TN system, STN system, IPS system, VA system, PSA system, PSVA system, and FFS system. It is more preferable to apply the method, the PSA method, the PSVA method, and the FFS method.

  The liquid crystal composition of the present invention may contain benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like as a polymerization initiator, if necessary.

  When the liquid crystal composition of the present invention has a positive dielectric anisotropy, the dielectric anisotropy (Δε) at 20 ° C. is 2.0 to 20.0, but 4.0 to 18.0 is 4.0 to 16.0 is more preferable, and 4.0 to 14.0 is particularly preferable.

  When the liquid crystal composition of the present invention has negative dielectric anisotropy, the dielectric anisotropy (Δε) at 20 ° C. is from −2.0 to −8.0, but from −2.0 to − 6.0 is preferable, -2.0 to -5.0 is more preferable, and -2.5 to -4.0 is particularly preferable.

  The liquid crystal composition of the present invention has a refractive index anisotropy (Δn) at 20 ° C. of 0.08 to 0.18, more preferably 0.09 to 0.15, and 0.09 to 0.12. Particularly preferred. More specifically, it is preferably 0.10 to 0.18 when dealing with a thin cell gap, and preferably 0.08 to 0.10 when dealing with a thick cell gap.

  The liquid crystal composition of the present invention has a viscosity (η) at 20 ° C. of 10 to 30 mPa · s, more preferably 10 to 25 mPa · s, and particularly preferably 10 to 20 mPa · s.

The liquid crystal composition of the present invention has a rotational viscosity (γ ₁ ) at 20 ° C. of 30 to 130 mPa · s, more preferably 30 to 110 mPa · s, and particularly preferably 40 to 90 mPa · s. .

The liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T _ni ) of 60 ° C to 120 ° C, more preferably 70 ° C to 110 ° C, and particularly preferably 70 ° C to 100 ° C.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

  In the examples, the measured characteristics are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: Refractive index anisotropy at 20 ° C. Δε: Dielectric anisotropy at 20 ° C. η: Viscosity at 20 ° C. (mPa · s)
γ1: rotational viscosity at 20 ° C. (mPa · s)
Drop mark: The drop mark of the liquid crystal display device was evaluated by the following four-step evaluation of the drop mark that appeared white when the entire surface was displayed in black.

◎: No dripping trace ○: Drip trace is acceptable but acceptable △: Drop trace is unacceptable level ×: Dripping trace is very poor level (side chain)
-F -F Fluorine atom
-OCF3 -OCF ₃
-n -C _n H _{2n + 1} linear alkyl group with n carbon atoms
n- C _n H _{2n + 1-} linear alkyl group with n carbon atoms
-On -OC _n H _{2n + 1} linear alkoxyl group with n carbon atoms
nO- C _n H _{2n + 1} O- Linear alkoxyl group with n carbon atoms
-V -CH = CH ₂
V- CH ₂ = CH-
-V1 -CH = CH-CH ₃
1V- CH ₃ -CH = CH-
-2V -CH ₂ -CH ₂ -CH = CH ₃
V2- CH ₃ = CH-CH ₂ -CH _2-
-2V1 -CH ₂ -CH ₂ -CH = CH-CH ₃
1V2- CH ₃ -CH = CH-CH ₂ -CH ₂
(Linking group)
-CF2O- -CF ₂ -O-
-OCF2- -O-CF _2-
-1O- -CH ₂ -O-
-O1- -O-CH _2-
-COO- -COO-
(Ring structure)

(Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3)
LC-1 (Liquid crystal composition 1), LC-2 (Liquid crystal composition 2) and LC-3 (Liquid crystal composition 3) were prepared, and their physical properties were measured.

  A liquid crystal display device was prepared by dropping and injecting these liquid crystal compositions. At this time, the evaluation of dropping marks was performed with or without a liquid crystal alignment aid, and the results were as follows. For the ITO glass substrate with a vertical alignment film, the alignment film for vertical alignment is applied to the ITO glass substrate with a thickness of about 100 nm by spin coating, baked at 80 ° C. for 5 minutes, and further baked at 240 ° C. for 40 minutes. I got it. The liquid crystal alignment aid was applied by spin coating.

  In the liquid crystal alignment aid 1 (DMI-1), 2% by mass of the compound represented by the formula (I-Af) as the first component, and 98% by mass of n-hexane as the hydrocarbon-based organic solvent as the second component. It was prepared with.

  When the liquid crystal alignment aid is not used (Comparative Example 1, Comparative Example 2 and Comparative Example 3), the liquid crystal composition is dropped in one drop filling (ODF: One Drop Fill) process. It was confirmed that there was a mark and the level was quite inferior (× evaluation).

In the case of using the liquid crystal alignment aid of the present invention (Example 1, Example 2 and Example 3), it was confirmed that the result was without dripping marks. That is, it was confirmed that dripping marks, which are the effects of the present invention, were completely eliminated or sufficiently suppressed. In addition, since no dripping marks were generated, a liquid crystal display element could be manufactured with high yield.
(Example 4, Example 5, Example 6, Example 7, Example 8, and Example 9)
Liquid crystal alignment aid 2 (DMI-2) is 1% by mass of the compound represented by the formula (I-Ab) as the first component, and 99% by mass of n-hexane as the hydrocarbon-based organic solvent as the second component. It was prepared with.

  Liquid crystal alignment aid 3 (DMI-3) is 1% by mass of the compound represented by the formula (I-Ac) as the first component, and 90% by mass of n-hexane as the hydrocarbon organic solvent as the second component. And 9% by weight of acetone.

  Liquid crystal alignment aid 4 (DMI-4) is 1% by mass of the compound represented by the formula (I-Am) as the first component, 90% by mass of hexane as the hydrocarbon-based organic solvent as the second component, and acetone. Was prepared at 9% by weight.

  The liquid crystal alignment aid 5 (DMI-5) is 1% by mass of the compound represented by the formula (I-Bc) as the first component, and 99% by mass of isopropyl alcohol as the hydrocarbon-based organic solvent as the second component. Prepared.

  In the liquid crystal alignment aid 6 (DMI-6), 1% by mass of the compound represented by the formula (I-Ca) as the first component and 99% by mass of n-hexane as the hydrocarbon organic solvent which is the second component. It was prepared with.

  In the case of using the liquid crystal alignment aid of the present invention (Example 4, Example 5, Example 6, Example 7, Example 8, and Example 9), it was confirmed that the results were without dripping marks. . That is, it was confirmed that dripping marks, which are the effects of the present invention, were completely eliminated or sufficiently suppressed. In addition, since no dripping marks were generated, a liquid crystal display element could be manufactured with high yield.

  Further, when 30 mass ppm of the formula (H-11) is added as the third component of the liquid crystal alignment aid 2 (DMI-2), no dripping marks are generated, and a liquid crystal display in which display defects such as image sticking are less likely to occur. An element was obtained.

  Further, when 50 mass ppm of the formula (H-12) is added as the third component of the liquid crystal alignment aid 2 (DMI-2), no dripping marks are generated, and a liquid crystal display in which display defects such as image sticking are less likely to occur. An element was obtained.

  Further, when 10 mass ppm of the formula (H-15) is added as the third component of the liquid crystal alignment aid 6 (DMI-6), no dripping marks are generated, and a liquid crystal display in which display defects such as image sticking are less likely to occur. An element was obtained.

Moreover, when 100 mass ppm of the formula (H-15) is added as the third component of the liquid crystal alignment aid 6 (DMI-6), no dripping marks are generated, and a liquid crystal display in which display defects such as image sticking are less likely to occur. An element was obtained.
(Example 10, Example 11, Example 12, Comparative Example 4, Comparative Example 5 and Comparative Example 6)
LC-4 (Liquid Crystal Composition 4) was prepared and measured for physical properties.

  A liquid crystal display device was produced by dropping and injecting this liquid crystal composition. At this time, the evaluation of dropping marks was performed with or without a liquid crystal alignment aid, and the results were as follows.

  In the liquid crystal alignment aid 7 (DMI-7), 2% by mass of the compound represented by the formula (I-Ad) as the first component and 98% by mass of n-hexane as the hydrocarbon-based organic solvent as the second component. It was prepared with.

  In the liquid crystal alignment aid 8 (DMI-8), 1% by mass of the compound represented by the formula (I-Ba) as the first component and 90% by mass of n-hexane as the hydrocarbon organic solvent which is the second component. And acetone was prepared at 9% by mass.

  Liquid crystal alignment aid 9 (DMI-9) is 1% by mass of the compound represented by the formula (I-Cc) as the first component, and 99% by mass of n-hexane as the hydrocarbon-based organic solvent as the second component. It was prepared with.

  Further, when 20 mass ppm of the formula (H-15) is added as the third component of the liquid crystal alignment aid 7 (DMI-7), no dripping marks are generated, and display defects such as image sticking are less likely to occur. An element was obtained.

  When the liquid crystal alignment aid is not used (Comparative Example 4, Comparative Example 5 and Comparative Example 6), the liquid crystal composition is dropped in one drop filling (ODF: One Drop Fill) process. It was confirmed that there was a mark and the level was quite inferior (× evaluation).

  In the case where the liquid crystal alignment aid of the present invention was used (Example 10, Example 11 and Example 12), it was confirmed that the result was without dripping marks. That is, it was confirmed that dripping marks, which are the effects of the present invention, were completely eliminated or sufficiently suppressed. In addition, since no dripping marks were generated, a liquid crystal display element could be manufactured with high yield.

Claims (8)

Liquid crystal alignment aid applied to alignment film for liquid crystal. Formula (I)

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms. represents a 10 alkenyloxy group having from one -CH 2 present in the radical _- or non-adjacent two or more -CH 2 _- may be replaced each independently -O- or -S- In addition, one or two or more hydrogen atoms present in the group may be each independently substituted with a fluorine atom or a chlorine atom, and ring A, ring B, and ring C are each independently , Trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4 A phenylene group, 2,3-difluoro-1, -Phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- 2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a hydrogen atom in the group may be substituted with a fluorine atom, Z ¹ and Z ² are , Each independently, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, -CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, _{-CH 2 CH 2 -COO -, -} CH 2 CH _2— OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CY ¹ = CY ² — (where Y ¹ and Y ² are , Each independently represents a fluorine atom or a hydrogen atom.), —C≡C— or a single bond, n represents 0, 1 or 2). The liquid crystal alignment aid as described. The liquid crystal alignment aid according to claim 1 or 2, further comprising an antioxidant. A liquid crystal alignment film using the liquid crystal alignment aid according to claim 1. A liquid crystal display element using the alignment film for liquid crystal according to claim 4. The liquid crystal display element according to claim 5, wherein the liquid crystal composition to be aligned by the liquid crystal alignment film contains one or more compounds represented by the following general formula (LC).

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one or more CH ₂ groups in the group are oxygen atoms. May be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that one or two of the groups The above hydrogen atoms may be optionally substituted with halogen atoms,
A ^LC1 and A ^LC2 are each independently
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more CH groups not adjacent to each other may be substituted with a nitrogen atom), and (c) 1 , 4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl A group or a group selected from the group consisting of a chroman-2,6-diyl group, but one or more hydrogen atoms contained in the group (a), group (b) or group (c) Each may be substituted with F, Cl, CF ₃ or OCF ₃ ,
Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, Represents —OCF ₂ —, —CF ₂ O—, —COO— or —OCO—,
Y ^LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one or more CH in the group _{The two} groups are —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF ₂ so that oxygen atoms are not directly adjacent to _{each other.} -One or more hydrogen atoms in the group may be optionally substituted with a halogen atom,
a represents an integer of 1 to 4, but a represents 2, 3 or 4, and when there are a plurality of ^ALC1 , the plurality of ^ALC1 may be the same or different, and ^ZLC is When there are a plurality of Z ^LCs , the plurality of Z ^LCs may be the same or different. ) The liquid crystal display element according to claim 6, wherein the liquid crystal composition further contains a polymer of a compound represented by one or more general formulas (M).

You may contain the polymeric compound represented by these by 1 type, or 2 or more types.
In General Formula (M), X ²⁰¹ and X ²⁰² each independently represent a hydrogen atom, a methyl group, or a —CF ₃ group. X ²⁰¹ and X ²⁰² are each preferably a diacrylate derivative that is a hydrogen atom, and a dimethacrylate derivative that is both a methyl group, and a compound in which one is a hydrogen atom and the other is a methyl group. A preferred compound can be used depending on the application, but in the PSA display element, the polymerizable compound represented by the general formula (M) preferably has at least one methacrylate derivative, and preferably has two.
In General Formula (M), Sp ²⁰¹ and Sp ²⁰² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 7). And an oxygen atom is bonded to the ring. In the PSA mode liquid crystal display element, at least one of Sp ²⁰¹ and Sp ²⁰² is preferably a single bond, both of which are single bonds or one of which is a single bond and the other is an alkylene having 1 to 8 carbon atoms. It is preferably a group or —O— (CH ₂ ) _s —. In this case, an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.
In general formula (M), ring M ²⁰¹ , ring M ²⁰² and ring M ²⁰³ are each independently a trans-1,4-cyclohexylene group (one or non-adjacent two or more —CH in the group). ₂ -may be substituted by -O- or -S-), 1,4-phenylene group (one or two or more non-adjacent -CH = in the group is substituted by -N =. 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a hydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and each hydrogen atom in the group is independently a fluorine atom, a -CF ₃ group, An alkyl group having 1 to 10 carbon atoms, 1 carbon atom To 10 alkoxyl groups or formula (R-1) to formula (R-15). An organic solvent solution of the liquid crystal alignment aid according to claim 1.