CN112852443A - Polymerizable liquid crystal composition and liquid crystal display element using same - Google Patents
Polymerizable liquid crystal composition and liquid crystal display element using same Download PDFInfo
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 188
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 229910052736 halogen Inorganic materials 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
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- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
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- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
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- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
- Liquid Crystal (AREA)
Abstract
The invention provides a polymerizable liquid crystal composition and a liquid crystal display element using the same. The invention provides a polymerizable liquid crystal composition having a large Delta epsilon, being stable to heat and light and capable of maintaining a high voltage holding ratio for a long time, and a liquid crystal display element using the polymerizable liquid crystal composition and having excellent display quality. The present invention aims to provide a polymerizable liquid crystal composition having negative dielectric anisotropy, which contains 1 or more polymerizable compounds having 1 or more polymerizable groups in 1 molecule, 1 or more polymerizable light stabilizers represented by general formula (H), and 1 or more liquid crystal compounds represented by general formula (II), and a liquid crystal display element using the same.
Description
Technical Field
The present invention relates to a polymerizable liquid crystal composition useful as an electro-optical liquid crystal display material and a liquid crystal display element using the same.
Background
Liquid crystal display elements have been used in watches, electronic calculators, various measuring devices, panels for automobiles, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display panels, and the like. Typical examples of liquid crystal display systems include TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical alignment) type characterized by vertical alignment using a TFT (thin film transistor), IPS (in-plane switching) type/FFS (fringe field switching) type characterized by horizontal alignment, and the like.
Among these display systems, IPS type, ECB type (Electrically Controlled Birefringence), VA type, CSH (color super homeotropic) type, and the like have a characteristic of using a liquid crystal material exhibiting a negative dielectric anisotropy (Δ ∈). All of these driving methods require low-voltage driving, high-speed response, and a wide operating temperature range. That is, it is required that Δ ∈ has a large absolute value, viscosity (η) is small, and nematic phase-isotropic liquid phase transition temperature (Tni) is high. In addition, it is necessary to adjust Δ n of the liquid crystal composition to an appropriate range in accordance with the setting of Δ n × d, which is the product of the refractive index anisotropy (Δ n) and the cell gap (d), in conjunction with the cell gap. In addition, in the case of applying a liquid crystal display element to a television or the like, high-speed response is important, and therefore, a liquid crystal composition having a small γ 1 is required. In order to optimize Δ ∈, Δ n, and the like for each display element, the liquid crystal composition is generally composed of several to several tens of compounds.
Among these, liquid crystal compositions required for high-speed response in liquid crystal television applications and the like are required to have sufficiently small η, sufficiently small γ 1, and large elastic constant (K33) without decreasing Δ n and Tni, and to have large Δ ∈ in order to realize low-voltage driving. In addition, the liquid crystal composition needs to exhibit a high Voltage Holding Ratio (VHR) in order to ensure reliability. This is because the liquid crystal display element is required to have excellent display quality without causing or suppressing display defects such as burn-in and display unevenness, and it is generally considered that a high Voltage Holding Ratio (VHR) is necessary to suppress such display defects.
Further, the liquid crystal composition is required to be stable against external stimuli such as moisture, air, heat, light, and the like. If stability against external stimuli is impaired, display defects such as burn-in and display unevenness are likely to occur in the liquid crystal display element. Particularly, in the case of manufacturing a liquid crystal display element using a polymer stabilization technique typified by a PSA (polymer stabilized alignment) technique, the liquid crystal composition is easily deteriorated by Ultraviolet (UV) irradiation at the time of panel formation, and thus stability of the liquid crystal composition and a compound constituting the same against external stimuli is strongly required.
In order to obtain stability of a liquid crystal composition and a compound constituting the same against external stimuli, it is known to add an additive such as a light stabilizer (patent documents 1 and 2).
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2014/208320
[ patent document 1] International publication No. 2018/123184
Disclosure of Invention
Problems to be solved by the invention
In order to obtain a liquid crystal composition having a large Δ ∈, it is useful to include, as a liquid crystal compound, a liquid crystal compound (hereinafter, referred to as a specific compound) having a structure in which a 1, 4-phenylene group substituted with fluorine at the 2-position and the 3-position is connected to another ring via a methoxy linking group and having a negative dielectric anisotropy Δ ∈. However, for example, when the above-mentioned specific compound is deteriorated by Ultraviolet (UV) irradiation or heat for a long time in polymerizing the polymerizable compound, Δ ∈ and VHR of the polymerizable liquid crystal composition are reduced. Therefore, a polymerizable liquid crystal composition containing the above-mentioned specific compound is required to have higher weather resistance. Further, although known Hindered Amine Light Stabilizers (HALS) have a function of capturing impurities that are a factor causing the reduction of VHR, there is a problem that the reduction of VHR cannot be sufficiently suppressed even if HALS is added.
The present invention addresses the problem of providing a polymerizable liquid crystal composition having a large Δ ∈ and being stable against heat and light and capable of maintaining a high voltage holding ratio for a long period of time, and a liquid crystal display element having excellent display quality using the polymerizable liquid crystal composition.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have found that the achievement of a high Δ ∈ and high reliability such as stability against external stimuli and long-term maintenance of a high VHR can be achieved at the same time by using a hindered amine compound having a polymerizable function as a light stabilizer in combination with a specific liquid crystal compound in a polymerizable liquid crystal composition containing a polymerizable compound, and have completed the present invention.
That is, the present invention provides a polymerizable liquid crystal composition having negative dielectric anisotropy, which comprises 1 or more polymerizable compounds having 1 or more polymerizable groups in 1 molecule, 1 or more light stabilizers represented by the general formula (H), and 1 or more liquid crystal compounds represented by the general formula (II).
[ solution 1]
(in the general formula (H), T is a group represented by the following formula (1),
[ solution 2]
(in the formula (1), Ra, Rb, Rc and Rd each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, Ra and Rb and/or Rc and Rd may be bonded to each other to form a ring,
rg represents a hydrogen atom, a hydroxyl group, -O-, or an alkyl group having 1 to 12 carbon atoms, and 1 or 2 or more-CH groups not adjacent to each other are present in the alkyl group2-independently of one another may be-O-, -S-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH-COO-, -CH-OCO-, -COO-CH-, -OCO-CH-, -CH-, -C.ident.C-、-Si(CH3)2-, trans-1, 4-cyclohexylene, 1, 4-phenylene or naphthalene-2, 6-diyl, 1 or 2 or more hydrogen atoms in Rg may be independently substituted with a halogen atom or a cyano group,
nT1and nT2Each independently represents 0, 1,2 or 3, nT1+nT2Represents 1,2,3 or 4, and the black dot represents a connecting bond. )
AH1And AH2Independently represent a 2-valent aromatic group, a 2-valent cycloaliphatic group, a 2-valent heterocyclic compound group, a 2-valent condensed ring and a 2-valent condensed polycyclic group, wherein more than 1 hydrogen atom in the ring structure can be replaced by a group LH1Or RH1-(AH3-ZH3)m H2-is substituted, AH1And AH2One of them may represent a single bond,
AH3represents a 2-valent aromatic group, a 2-valent cycloaliphatic group, a 2-valent heterocyclic compound group, a 2-valent condensed ring and a 2-valent condensed polycyclic ring, wherein more than 1 hydrogen atom in the ring structure can be replaced by a group LH1The substitution is carried out by the following steps,
ZH1、ZH2and ZH3Independently represent-O-, -S-, -CO-O-, -O-CO-O-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n-、-CF2CH2-、-CH2CF2-、-(CF2)n-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH2-CH2-CO-O-、-O-CO-CH2-CH2-、-CRH2RH3-or single bonds, in which more than one hydrogen atom may be replaced by a group LH1Or RH1-(AH3-ZH3)m H2-a substitution of a group of formula (I),
LH1represents PH2-SpH2-, a group T, a fluorine atom, a chlorine atom, a cyano group, or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms1 or more non-adjacent-CH2May be substituted by-O-, -S-, -CO-O-, -O-CO-O-in such a way that oxygen atoms and/or sulfur atoms are not linked directly to one another, and 1 or more hydrogen atoms in the alkyl group may be replaced by fluorine atoms, chlorine atoms or PH2-SpH2-a substitution of a group of formula (I),
PH1and PH2Each independently represents a hydrogen atom or a polymerizable group,
SpH1and SpH2Each independently represents a spacer or a single bond,
RH1represents PH2-SpH2A hydrogen atom, a fluorine atom, a chlorine atom, or a C1-25 linear, branched or cyclic alkyl group, wherein at least 1 of the alkyl groups is not adjacent to a-CH2May be substituted by-O-, -S-, -CO-O-, -O-CO-O-in such a way that oxygen atoms and/or sulfur atoms are not linked directly to one another, and 1 or more hydrogen atoms in the alkyl group may be replaced by fluorine atoms, chlorine atoms or P atomsH2-SpH2-a substitution of a group of formula (I),
RH2and RH3Each independently represents a hydrogen atom or an alkylene group having 1 to 12 carbon atoms,
mH1represents 0, 1,2,3 or 4,
mH2represents 0, 1,2,3 or 4,
n represents 1,2,3 or 4,
PH2、SpH2、LH1、AH1、AH2、AH3、ZH2、ZH3、RH1and T, the symbols may be the same or different,
wherein the general formula (H) has 1 or more polymerizable groups in the molecule. )
[ solution 3]
(in the formula, RII1And RII2Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groupsOr 2 or more-CH not adjacent2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,
AII1、AII2and AII3Each independently represents a group selected from the group consisting of,
(a)1, 4-cyclohexylene (1-CH present in the radical)2-or 2 or more-CH not adjacent2-may be substituted by-O-. ) A
(b)1, 4-phenylene (1-CH or not adjacent 2 or more-CH present in the radical may be substituted by-N) -),
(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-N ═ and)
(d)1, 4-Cyclohexenylene group
The aforementioned group (a), group (b), group (c) and group (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,
ZII1and ZII2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,
nII1and nII2Each independently represents an integer of 0 to 2, nII1+nII2Is a number of 0, 1 or 2,
AII1and AII2When a plurality of the compounds are present, they may be the same or different,
ZII1and ZII2When a plurality of the compounds are present, they may be the same or different. )
The present invention also provides a liquid crystal display element using a polymerizable liquid crystal composition having a negative dielectric anisotropy, the polymerizable liquid crystal composition containing 1 or more polymerizable compounds having 1 or more polymerizable groups in 1 molecule, 1 or more light stabilizers represented by general formula (H), and 1 or more liquid crystal compounds represented by general formula (II).
ADVANTAGEOUS EFFECTS OF INVENTION
The polymerizable liquid crystal composition of the present invention has a large Δ ∈ and is stable against external stimuli such as heat and light, and can maintain a high voltage holding ratio for a long time even when subjected to a polymer stabilization step associated with a UV irradiation step or left to stand under severe storage conditions. In addition, the liquid crystal display element of the present invention has excellent display quality without causing or suppressing display failure by using the polymerizable liquid crystal composition.
Drawings
Fig. 1 is a schematic diagram showing an example of a liquid crystal display element of the present invention.
Description of the symbols
1: a liquid crystal display element; 2: a first substrate; 3: a second substrate; 4: a liquid crystal layer; 5: a pixel electrode layer; 6: a common electrode layer; 7. 8: a polarizing plate; 9: and a color filter.
Detailed Description
I. Polymerizable liquid crystal composition
The polymerizable liquid crystal composition of the present invention comprises 1 or more polymerizable compounds having 1 or more polymerizable groups in 1 molecule, 1 or more light stabilizers represented by general formula (H), and 1 or more liquid crystal compounds represented by general formula (II), and has negative dielectric anisotropy.
According to the polymerized liquid crystal composition of the present invention, a high Δ ∈ can be realized by the liquid crystal compound represented by the above general formula (II), and further, by capturing impurities generated from the compound represented by the general formula (II) and other compounds by external stimulus by the light stabilizer represented by the general formula (H), reduction of VHR due to the generation of the impurities can be suppressed.
Further, the polymerizable liquid crystal composition of the present invention contains a polymerizable compound and a light stabilizer represented by the general formula (H), and thus can suppress the reduction of VHR due to the presence of the light stabilizer. In detail, although a hindered amine-based light stabilizer commonly used in a conventional liquid crystal composition does not have a polymerization function (i.e., a polymerizable group), such a non-polymerizable light stabilizer has an effect of improving reliability by trapping impurities in a liquid crystal layer, and on the other hand, the compound itself becomes an ion conduction source due to its large polarity, and VHR is lowered. On the other hand, the light stabilizer represented by the general formula (H) has at least 1 polymerizable group in the molecular structure, and when the polymerizable compound is polymerized by irradiating the polymerizable liquid crystal composition with ultraviolet light, the polymerizable group of the light stabilizer represented by the general formula (H) reacts with a part of the polymerizable compound. It is presumed that the light stabilizer represented by the general formula (H) is incorporated into the polymerized layer formed by polymerization of the polymerizable compound. The light stabilizer represented by the general formula (H) introduced into the polymerization layer retains the function of trapping impurities and does not function as an ion conduction source, and therefore, the reduction of VHR can be more effectively suppressed than the case of using a non-polymerizable light stabilizer. Thus, the polymerizable liquid crystal composition of the present invention can achieve both a high Δ ∈ and a high VHR.
The polymerizable liquid crystal composition of the present invention exhibits negative dielectric anisotropy (Δ ∈), and the absolute value | Δ ∈ | of the polymerizable liquid crystal composition is 2 or more. The dielectric anisotropy (. DELTA.. di-elect cons.) of the polymerizable liquid crystal composition of the present invention at 20 ℃ is preferably-2 or less, preferably in the range of-2.0 to-8.0, more preferably in the range of-2.0 to-5.0, and particularly preferably in the range of-2.5 to-5.0.
In the present specification, the light stabilizer represented by the general formula (H) may be referred to as a compound represented by the general formula (H) or a compound (H). The liquid crystal compound represented by the general formula (II) may be referred to as only the compound represented by the general formula (II) or the compound (II).
The light stabilizer represented by the general formula (H) has a polymerizable group in its molecular structure, but is not contained in the polymerizable compound described later. Among the light stabilizers, the light stabilizer represented by the general formula (H) is referred to as a "polymerizable light stabilizer", and the light stabilizer having no polymerizable group is referred to as a "non-polymerizable light stabilizer".
In the present specification, a polymerizable compound is removed from a polymerizable liquid crystal composition to obtain a product, which is referred to as a liquid crystal composition. That is, the polymerizable liquid crystal composition of the present invention includes a liquid crystal composition containing 1 or more light stabilizers represented by the general formula (H) and 1 or more liquid crystal compounds represented by the general formula (II), and 1 or more polymerizable compounds having 1 or more polymerizable groups in 1 molecule.
Further, a liquid crystal composition from which the light stabilizer represented by the general formula (H) and other additives are removed may be referred to as a base composition.
(1) Liquid crystal composition
The liquid crystal composition of the present invention preferably exhibits negative dielectric anisotropy. The preferred range of the value of the dielectric anisotropy of the liquid crystal composition of the present invention may be the same as the range of the dielectric anisotropy of the polymerizable liquid crystal composition of the present invention described above.
The constituent components of the liquid crystal composition of the present invention are explained below.
(light stabilizer represented by the general formula (H))
The liquid crystal composition of the present invention contains 1 or more light stabilizers represented by the general formula (H).
[ solution 4]
In the general formula (H), T is a group represented by the following formula (1). Namely, T represents a hindered amine skeleton.
[ solution 5]
In the formula (1), Ra, Rb, Rc and Rd independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and Ra and Rb and/or Rc and Rd may be bonded to each other to form a ring.
Among them, Ra, Rb, Rc and Rd are each independently preferably a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Specifically, Ra, Rb, Rc and Rd are each independently preferably a group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. From the viewpoint of stability, Ra, Rb, Rc and Rd are each independently preferably a branched alkyl group, preferably sec-butyl or tert-butyl. In addition, Ra, Rb, Rc, and Rd are each independently particularly preferably a methyl group from the viewpoint of availability of raw materials and stability of the compound. In order to easily remove polar impurities mixed during production, Ra and Rb and/or Rc and Rd may be connected to each other to form a ring structure.
In the formula (1), Rg represents a hydrogen atom, a hydroxyl group, -O-, or an alkyl group having 1 to 12 carbon atoms, and 1 or 2 or more-CH groups which are not adjacent to each other are present in the alkyl group2-independently from each other may be-O-, -S-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH-COO-, -CH-OCO-, -COO-CH-, -OCO-CH-, -CH-, -C.ident.C-, -Si (CH ≡ C)3)2-, trans-1, 4-cyclohexylene, 1, 4-phenylene or naphthalene-2, 6-diyl, wherein 1 or 2 or more hydrogen atoms in Rg may be independently substituted with a halogen atom or a cyano group, respectively.
Among them, Rg preferably represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms or a benzyl group. From the viewpoint of improving the ability to prevent photodegradation, Rg preferably represents a hydrogen atom or a hydroxyl group, and particularly preferably represents a hydrogen atom. In addition, Rg preferably represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 3 to 6 carbon atoms from the viewpoint of compatibility with the liquid crystal compound and the polymerizable compound. The alkyl group and the alkenyl group may be linear or branched, and are preferably linear.
In the above formula (1), nT1And nT2Each independently represents 0, 1,2 or 3, nT1+nT2Represents 1,2,3 or 4. Among them nT1And nT2Each independently preferably represents 1 or 2. In addition, nT1+nT2Preferably 1 or 2, particularly preferably 2.
In the formula (1), the black dots represent connecting bonds.
In the general formula (1), when there are a plurality of T, the plurality of T may be the same or different.
In the general formula (H), PH1Represents a hydrogen atom or a polymerizable group. The polymerizable group is preferably represented by any one of the following formulae (P-1) to (P-17).
[ solution 6]
Among them PH1Preferably a hydrogen atom or a group represented by the formula (P-1), the formula (P-2), the formula (P-5), the formula (P-6), the formula (P-8), the formula (P-12), the formula (P-14) or the formula (P-17), more preferably a hydrogen atom or a group represented by the formula (P-1), the formula (P-2), the formula (P-8), the formula (P-12) or the formula (P-14), and still more preferably a hydrogen atom or a group represented by the formula (P-1) or the formula (P-2).
In addition, since the general formula (H) has 1 or more polymerizable groups in the molecule, when m isH1Is 0 and ZH1When it is a single bond, PH1Represents a polymerizable group. In addition, when mH1Is 1,2,3 or 4 and AH1、AH2、ZH1And ZH2When none of them has a polymerizable group, PH1Represents a polymerizable group.
In the general formula (H), SpH1Represents a spacer group or a single bond. The spacer represents a linear or branched alkylene group having 1 to 12 carbon atoms, 1-CH in the alkylene group2-or 2 or more-CH not adjacent2-may be substituted by-O-, -COO-, -OCO-, -CH ═ CH-, or-C ≡ C-. Among them SpH1Preferably represents a single bond or a linear alkylene group having 1 to 12 carbon atoms (1 or not less than 2-CH groups not adjacent to each other in the group)2-may be substituted by-O-, -COO-or-OCO-. ) Preferably represents a single bond or a linear alkylene group having 1 to 6 carbon atoms (1 or not less than 2-CH groups not adjacent to each other in the group)2-may be substituted by-O-, -COO-or-OCO-. ) Preferably represents a single bond or a linear alkylene group having 2 to 4 carbon atoms (1 or not less than 2-CH groups not adjacent to each other in the group)2-may be substituted by-O-, -COO-or-OCO-. ) Particularly preferably a single bond。
In the general formula (H), AH1And AH2Independently represent a 2-valent aromatic group, a 2-valent cycloaliphatic group, a 2-valent heterocyclic compound group, a 2-valent condensed ring and a 2-valent condensed polycyclic group, wherein more than 1 hydrogen atom in the ring structure can be replaced by a group LH1Or RH1-(AH3-ZH3)m H2-is substituted, AH1And AH2One of them may represent a single bond. Note that, for the group LH1And RH1-(AH3-ZH3)m H2-as described hereinafter.
Wherein A isH1And AH2Each independently preferably represents a 2-valent 6-membered ring aromatic group or a 2-valent 6-membered ring aliphatic group (in which 1 or more hydrogen atoms may be replaced by the group L)H1Or RH1-(AH3-ZH3)m H2-substitution). In addition, AH1And AH2In AH1Preferably a single bond. Specifically, A is preferredH1And AH2Each independently represents a group selected from the group consisting of,
(a)1, 4-cyclohexylene (1-CH present in the radical)2-or 2 or more-CH not adjacent2-may be substituted by-O-. ) A
(b)1, 4-phenylene (1-CH or not adjacent 2 or more-CH present in the radical may be substituted by-N) -),
(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-N ═ and)
(d)1, 4-Cyclohexenylene group
(the aforementioned group (a), group (b), group (c) and group (d) may each independently be replaced by a group LH1Or RH1-(AH3-ZH3)m H2-substituted) or AH1Represents a single bond. Among them, A is more preferableH1And AH2Each independently represents 1, 4-cyclohexylene (1-CH present in the radical)2-or notAdjacent 2 or more-CH2-may be substituted by-O-. ) Or may be substituted by a group LH1Or RH1-(AH3-ZH3)m H2-substituted 1, 4-phenylene, or AH1Represents a single bond.
AH1And AH2When there are plural each, each AH1And each AH2Each may be the same or different.
In the general formula (H), ZH1And ZH2Independently represent-O-, -S-, -CO-O-, -O-CO-O-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n-、-CF2CH2-、-CH2CF2-、-(CF2)n-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH2-CH2-CO-O-、-O-CO-CH2-CH2-、-CRH2RH3-or single bonds, in which more than one hydrogen atom may be replaced by a group LH1Or RH1-(AH3-ZH3)m H2-substitution.
ZH1And ZH2In, RH2And RH3Each independently represents a hydrogen atom or an alkylene group having 1 to 12 carbon atoms.
In addition, ZH1And ZH2In the formula, n represents 1,2,3 or 4.
Wherein Z isH1Preferably represents-COO-, -OCO-or a single bond, more preferably a single bond. In addition, ZH2Preferably represents-COO-, -OCO-or a single bond. ZH2When there are plural, plural ZH2May be the same or different.
In the general formula (H), LH1Represents PH2-SpH2-, a group T, a fluorine atom, a chlorine atom, a cyano group, or a C1-25 linear, branched or cyclic alkyl group, wherein at least 1 of the alkyl groups is not adjacent to a-CH2May be in such a way that the oxygen atoms and/or the sulfur atoms are not directly linked to each otherSubstituted by-O-, -S-, -CO-O-, -O-CO-O-, and in addition, more than 1 hydrogen atom in the alkyl can be replaced by fluorine atom, chlorine atom or PH2-SpH2-substitution. The group T is a group represented by the above general formula (1).
Among them LH1Preferably represents PH2-SpH2A group T, a fluorine atom, a chlorine atom, a cyano group, a straight or branched alkyl group having 1 to 25 carbon atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or an alkoxycarbonyloxy group, wherein 1 or more hydrogen atoms in the group may be substituted by a fluorine atom or a chlorine atom. L isH1When there are plural, plural LH1May be the same or different.
In the general formula (H), PH2Represents a hydrogen atom or a polymerizable group. PH2The polymerizable group represented by the formula and the above PH1The polymerizable group represented by the formula (P-1) is preferably represented by any one of the formulae (P-1) to (P-17), and among these, a hydrogen atom or a group represented by the formula (P-1), the formula (P-2), the formula (P-5), the formula (P-6), the formula (P-8), the formula (P-12), the formula (P-14) or the formula (P-17) is preferable, a hydrogen atom or a group represented by the formula (P-1), the formula (P-2), the formula (P-8), the formula (P-12) or the formula (P-14) is more preferable, and a hydrogen atom or a group represented by the formula (P-1) or the formula (P-2) is even more preferable. PH2When there are plural, plural PH2May be the same or different.
In the general formula (H), SpH2Represents a spacer group or a single bond. The spacer represents a linear or branched alkylene group having 1 to 12 carbon atoms, 1-CH in the alkylene group2-or 2 or more-CH not adjacent2-may be substituted by-O-, -COO-, -OCO-, -CH ═ CH-, or-C ≡ C-. Among them SpH2Preferably represents a single bond or 1 or 2 or more-CH groups which are not adjacent to each other2A linear alkylene group having 1 to 12 carbon atoms which may be substituted with-O-, -COO-or-OCO-, preferably represents 1 or 2 or more-CH groups which are not adjacent to each other in a single bond or a group2A linear alkylene group having 1 to 6 carbon atoms which may be substituted with-O-, -COO-or-OCO-, preferably represents 1 or 2 or more-CH groups which are not adjacent to each other2-C2E c optionally substituted by-O-, -COO-or-OCO-4 is a linear alkylene group. SpH2When there are more than one, more than one SpH2May be the same or different.
In the general formula (H), RH1Represents PH2-SpH2A hydrogen atom, a fluorine atom, a chlorine atom, or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms. In the alkyl group, 1 or more non-adjacent-CH2May be substituted by-O-, -S-, -CO-O-, -O-CO-O-in such a way that oxygen atoms and/or sulfur atoms are not linked directly to one another. In the alkyl group, 1 or more hydrogen atoms may be each independently fluorine atom, chlorine atom or PH2-SpH2-substitution. RH1When there are plural, plural RH1May be the same or different.
In the general formula (H), AH3Represents a 2-valent aromatic group, a 2-valent cycloaliphatic group, a 2-valent heterocyclic compound group, a 2-valent condensed ring and a 2-valent condensed polycyclic ring, wherein more than 1 hydrogen atom in the ring structure can be replaced by a group LH1And (4) substitution.
Wherein A isH3Preferably represents a 6-membered cyclic aromatic group having a valence of 2 or a 6-membered cyclic aliphatic group having a valence of 2 (1 or more hydrogen atoms in the group may be replaced by the group L)H1Substitution). Specifically, AH3Preferably represents a group selected from the group consisting of the following.
(a)1, 4-cyclohexylene (1-CH present in the radical)2-or 2 or more-CH not adjacent2-may be substituted by-O-. ) A
(b)1, 4-phenylene (1-CH or not adjacent 2 or more-CH present in the radical may be substituted by-N) -),
(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-N ═ and)
(d)1, 4-Cyclohexenylene group
(the aforementioned group (a), group (b), group (c) and group (d) may each independently be replaced by a group LH1And (4) substitution. ). More preferably, AH3Represents optionally substituted 1, 4-cyclohexylene group (present in the radical)1-CH in the clique2-or 2 or more-CH not adjacent2-may be substituted by-O-. ) Or a group LH1Substituted 1, 4-phenylene.
AH3When there are plural, plural AH3May be the same or different.
In the general formula (H), ZH3represents-O-, -S-, -CO-O-, -O-CO-O-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n-、-CF2CH2-、-CH2CF2-、-(CF2)n-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH2-CH2-CO-O-、-O-CO-CH2-CH2-、-CRH2RH3-or a single bond. RH2And RH3And n is and ZH1And ZH2R in (1)H2And RH3And n is the same as defined above.
ZH3When there are plural, plural ZH3May be the same or different.
In the general formula (H), mH1Represents 0, 1,2,3 or 4. M among themH1Preferably represents 0, 1,2 or 3, more preferably 0, 1 or 2, still more preferably 0 or 1, and particularly preferably 0, from the viewpoint of stability.
mH1When it is 0, Z is preferablyH1And SpH1Are all single bonds, PH1Represents a polymerizable group. This is because the compound represented by the general formula (H) has a structure in which a polymerizable group is directly linked to T, i.e., a hindered amine skeleton in the formula, and thus the amount of the hindered amine skeleton per unit mass can be increased, and therefore, the reliability can be effectively improved even with a small amount of the compound added.
In addition, mH2Represents 0, 1,2,3 or 4. M among themH2Preferably represents 0, 1,2 or 3, more preferably represents 0, 1 or 2, still more preferably represents 0 or 1, and particularly preferably represents 0 from the viewpoint of stability.
The general formula (H) has 1 or more polymerizable groups in the molecule. The number of the polymerizable groups may be 1,2, or 3 or more. The number of the polymerizable groups may be large, but is preferably 3 or less, and more preferably 2 or less. If the number of polymerizable groups is too large, the molecular weight of the compound represented by the general formula (H) increases, the amount of hindered amine skeleton decreases relatively, and it becomes difficult to obtain the effect of improving reliability.
In addition, mH1Is 1 or more and PH1When representing a hydrogen atom, A is preferredH1、AH2、ZH1And ZH2Has a structure containing PH2-SpH2- (wherein P)H2Is a polymerizable group). Among them, A is preferableH1And AH2Has at least one group containing PH2-SpH2- (wherein P)H2Is a polymerizable group). On the other hand, mH1When 0, PH1Preferably, it represents a polymerizable group.
The light stabilizer represented by the general formula (H) is preferably a compound represented by the following general formula (H-1).
[ solution 7]
(in the general formula (H-1), Ra, Rb, Rc, Rd and Rg are the same as those defined for Ra, Rb, Rc, Rd and Rg in the general formula (H), respectively, PH1、SpH1、AH2、ZH2And mH1Are each independently of P in the general formula (H)H1、SpH1、AH2、ZH2And mH1The same definition. )
In the general formula (H-1), mH1When 0, PH1Represents a polymerizable group. Among them PH1Preferably represented by any one of the above-mentioned formulae (P-1) to (P-17), more preferably represented by formula (P-1) or formula (P-2).
The polymerizable liquid crystal composition of the present invention contains 1 or more light stabilizers represented by the general formula (H), and may further contain 1 or more other known light stabilizers together with the light stabilizers represented by the general formula (H). Examples of the known light stabilizer include a known light stabilizer having no polymerizable group (non-polymerizable stabilizer).
The lower limit of the total content of the compounds represented by the general formula (H) is preferably 0.001 mass%, 0.005 mass%, 0.01 mass%, 0.05 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the total content of the compounds represented by the general formula (H) is preferably 0.2 mass%, 0.15 mass%, or 0.1 mass% with respect to the total amount of the liquid crystal composition of the present invention. By setting the content of the compound represented by the general formula (H) within the above range, it is possible to not only sufficiently exert the function as a light stabilizer but also suppress the reduction of VHR.
Specifically, the total content of the compound represented by the general formula (H) is preferably in the range of 0.001 to 0.2% by mass, more preferably in the range of 0.005 to 0.15% by mass, and still more preferably in the range of 0.01 to 0.1% by mass, based on the total amount of the liquid crystal composition of the present invention.
(liquid crystal compound represented by the general formula (II))
The polymerizable liquid crystal composition of the present invention contains 1 or more kinds of compounds having 2 rings of-CH in the molecular structure2A liquid crystal compound having a linking part wherein linking groups represented by O-are linked. Specifically, the polymerizable compound of the present invention contains 1 or more liquid crystal compounds represented by the general formula (II).
[ solution 8]
(in the formula, RII1And RII2Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 or 2 or more-CH groups not adjacent to each other in the alkyl group2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,
AII1、AII2and AII3Respectively independent earth surfaceA group selected from the group consisting of,
(a)1, 4-cyclohexylene (1-CH present in the radical)2-or 2 or more-CH not adjacent2-may be substituted by-O-. ) A
(b)1, 4-phenylene (1-CH or not adjacent 2 or more-CH present in the radical may be substituted by-N) -),
(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-N ═ and)
(d)1, 4-Cyclohexenylene group
The aforementioned group (a), group (b), group (c) and group (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,
ZII1and ZII2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,
nII1and nII2Each independently represents an integer of 0 to 2, nII1+nII2Is a number of 0, 1 or 2,
AII1and AII2When a plurality of the compounds are present, they may be the same or different,
ZII1and ZII2When a plurality of the compounds are present, they may be the same or different. )
The polymerizable liquid crystal composition of the present invention is obtained by bonding a compound represented by the general formula (II), in other words, a compound having fluorine atoms substituted for the hydrogen atoms at the 2-and 3-positions in the 1, 4-phenylene group to which-CH is bonded2A compound having the structure of an O-linking group is an essential component, and can exhibit a high Δ ∈. The polymerizable liquid crystal composition of the present invention can exhibit excellent low-temperature storage stability by containing the compound, and a liquid crystal display element obtained using the polymerizable liquid crystal composition can exhibit low-voltage driving, a high response speed, andhigh VHR.
The compound represented by the general formula (II) is preferably a compound having negative Δ ∈ and an absolute value of more than 3.
In the general formula (II), RII1And RII2Each independently preferably represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and preferably represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Among them, at least RII2Preferably represents an alkoxy group having 1 to 4 carbon atoms, and more preferably represents an ethoxy group, a propoxy group or a butoxy group.
In the general formula (II), nII1Preferably represents 0 or 1. On the other hand, nII2Preferably represents 0.
The liquid crystal compound represented by the general formula (II) is preferably a compound selected from the group consisting of compounds represented by the following general formulae (II-1) and (II-2), and among these, a compound represented by the general formula (II-1) is preferable.
[ solution 9]
(in the formula, RII11And RII12Each independently represents R in the general formula (II)II1Same meaning as RII21And RII22Each independently represents R in the general formula (II)II2Same meaning, nII11Represents 0 or 1, nII12Represents 0 or 1, nII22Represents 1 or 2. A. theII11、AII12And AII22When a plurality of the compounds are present, they may be the same or different. )
The compound represented by the general formula (II-1) is preferably a compound selected from the group consisting of compounds represented by the following general formula (II-1-1) to the following general formula (II-1-5).
[ solution 10]
(in the formula, RII11And RII21Each independently represents R in the general formula (II)II1And RII2The same meaning is used. )
RII11And RII21Each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Among these, R is preferredII11And RII21In (A) at least RII21Is an alkoxy group having 1 to 4 carbon atoms, and R is more preferablyII21An alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group. RII21When it is an alkoxy group, the compound represented by the general formula (II-1) has a 1, 4-phenylene group substituted with fluorine at the 2-and 3-positions and-CH as a linking group2Oxygen atom of O-and RII21The oxygen atom of the alkoxy group (b) is directly bonded to the structure, and therefore, a higher Δ ∈ can be expressed. On the other hand, in the above-described structure, the spread of the electron cloud becomes large (the conjugated system spreads), and the absorption wavelength shifts to the long wavelength direction, and as a result, the absorption efficiency of ultraviolet rays increases, and light energy is easily received, and VHR may decrease due to the generation of impurities. In contrast, according to the present invention, by using the polymerizable light stabilizer represented by the general formula (H) in combination, it is possible to achieve a high VHR by increasing Δ ε and suppressing photodegradation using the compound represented by the general formula (II-1) having the above structure.
In addition, RII11Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.
The compound represented by the general formula (II-1) is particularly preferably a compound selected from the group consisting of compounds represented by the general formula (II-1-1) and compounds represented by the general formula (II-1-2).
The compounds represented by the general formula (II-1-1) and the general formula (II-1-2) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kinds of the compounds used are, for example, 1,2,3,4, 5 or more.
With respect to the general formula (II-1-1) and the general formulaThe content of each compound represented by (II-1-2) is preferably set to be higher when improvement of. DELTA.. di-elect cons.NIThe effect is good if the setting is higher. Further, when the dropping marks and the burn-in characteristics are improved, the content ranges of the compounds represented by the general formulae (II-1-1) to (II-1-5) are preferably set to be intermediate.
The lower limit of the content of the compound represented by the general formula (II-1-1) is preferably 1%, 2%, 5%, 10%, 13%, 15%, 17%, 20% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content of the above-mentioned compound is preferably 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% with respect to the total amount of the liquid crystal composition of the present invention.
The lower limit of the content of the compound represented by the general formula (II-1-2) is preferably 5%, 10%, 13%, 15%, 17%, 20%, 25%, 30% in the liquid crystal composition of the present invention. The upper limit of the content of the above-mentioned compound is preferably 50%, 45%, 40%, 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (II-1-1) is preferably a compound selected from the group consisting of compounds represented by the formulae (II-1-1.1) to (II-1-1.14), preferably compounds represented by the formulae (II-1-1.1) to (II-1-1.5), preferably compounds represented by the formulae (II-1-1.1) and (II-1-1.2).
[ solution 11]
The compounds represented by the general formulae (II-1-1.1) and (II-1-1.2) may be used alone or in combination, and the lower limit of the preferred content of these compounds alone or in combination with respect to the total amount of the composition of the present invention is 2%, 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferred amounts is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% with respect to the total amount of the composition of the invention.
Further, the compound represented by the general formula (II-1-2) is preferably a compound selected from the group consisting of the compounds represented by the formulae (II-1-2.1) to (II-1-2.14), preferably a compound represented by the formulae (II-1-2.1) to (II-1-2.4), preferably a compound represented by the formulae (II-1-2.2) and (II-1-2.4).
[ solution 12]
The compounds represented by the general formulae (II-1-2.2) and (II-1-2.4) may be used alone or in combination, and the lower limit of the preferable content of these compounds alone or in combination with respect to the total amount of the liquid crystal composition of the present invention is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
More specifically, the compound represented by the general formula (II-2) may be a compound selected from the group consisting of the compounds represented by the following general formula (II-2-1) and general formula (II-2-2).
[ solution 13]
(in the formula, RII12And RII22Each independently represents R in the general formula (II)II1And RII2The same meaning is used. )
RII12And RII22Each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.
The compounds represented by the general formula (II-2-1) and the general formula (II-2-2) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kinds of the compounds used are, for example, 1,2,3,4, 5 or more.
The content of each of the compounds represented by the general formulae (II-2-1) and (II-2-2) is preferably set higher when importance is placed on the improvement of. DELTA.. epsilon., preferably set higher when importance is placed on the solubility at low temperatures, and preferably set higher when importance is placed on TNIThe effect is good when the content is set to be higher. Further, when the dropping marks and the burn-in characteristics are improved, the content ranges of the compounds represented by the general formulae (II-2-1) and (II-2-2) are preferably set to be intermediate.
The lower limit of the content of the compound represented by the formula (II-2-1) is preferably 5% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, and 20% by mass or more, based on the total amount of the liquid crystal composition of the present invention. The upper limit of the content of the above-mentioned compound is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The lower limit of the content of the compound represented by the formula (II-2-2) is preferably 5% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, and 20% by mass or more, based on the total amount of the liquid crystal composition of the present invention. The upper limit of the content of the above-mentioned compound is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The total content of the compounds represented by the general formula (II) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, based on the total amount of the liquid crystal composition of the present invention. The total content of the compounds represented by the general formula (II) is preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less, based on the total amount of the liquid crystal composition of the present invention. The preferable range of the above total content can be appropriately set according to these upper and lower limits.
The content of the compound represented by the general formula (II) is, specifically, in the range of 10 to 70 mass%, preferably in the range of 20 to 50 mass%, and more preferably in the range of 30 to 40 mass% with respect to the total amount of the liquid crystal composition of the present invention.
(other liquid Crystal Compound)
The polymerizable liquid crystal composition of the present invention may further contain, as the liquid crystal compound, 1 or more compounds selected from the group of compounds represented by general formulae (N-1), (N-2) and (N-3) (excluding the compound represented by general formula (II)).
[ solution 14]
(in the above general formulae (N-1), (N-2) and (N-3), RN11、RN12、RN21、RN22、RN31And RN32Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 or 2 or more-CH groups not adjacent to each other in the alkyl group2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-, aN11、AN12、AN21、AN22、AN31And AN32Each independently represents a group selected from the group consisting of,
(a)1, 4-cyclohexylene (1-CH present in the radical)2-or 2 or more-CH not adjacent2-may be substituted by-O-. ) A
(b)1, 4-phenylene (1-CH or not adjacent 2 or more-CH present in the radical may be substituted by-N) -),
(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-N ═ and)
(d)1, 4-Cyclohexenylene group
The aforementioned group (a), group (b), group (c) and group (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,
ZN11、ZN12、ZN21、ZN22、ZN31and ZN32Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,
XN21represents a hydrogen atom or a fluorine atom,
TN31represents-CH2-or an oxygen atom,
nN11、nN12、nN21、nN22、nN31and nN32Each independently represents an integer of 0 to 3, nN11+nN12、nN21+nN22And nN31+nN32Each independently represents 1,2 or 3,
AN11～AN32、ZN11～ZN32when a plurality of the compounds are present, they may be the same or different. Wherein the compound represented by the general formula (II) is excluded. )
The compound represented by any one of the general formulae (N-1), (N-2) and (N-3) is preferably a compound having negative Δ ε and an absolute value of greater than 3.
In the general formulae (N-1), (N-2) and (N-3), RN11、RN12、RN21、RN22、RN31And RN32Independently preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, more preferably a carbon atomThe alkyl group having 1 to 5 carbon atoms or the alkenyl group having 2 to 5 carbon atoms, more preferably the alkyl group having 2 to 5 carbon atoms or the alkenyl group having 2 to 3 carbon atoms, and particularly preferably the alkenyl group having 3 carbon atoms (propenyl group).
When the ring structure to which the compound is bonded is a phenyl group (aromatic group), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and an alkenyl group having 4 to 5 carbon atoms are preferable, and when the ring structure to which the compound is bonded is a saturated ring structure such as cyclohexane, pyran, dioxane, or the like, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms when present is preferably 5 or less, and is preferably linear.
The alkenyl group is preferably selected from groups represented by any one of formulae (R1) to (R5) (the black dot in each formula represents a connecting bond).
[ solution 15]
AN11、AN12、AN21、AN22、AN31And AN32Each independently preferably represents a trans-1, 4-cyclohexylene group, 1, 4-phenylene group, 2-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 ] aliphatic group for improving the response speed]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, more preferably represents the following structure,
[ solution 16]
More preferably, it represents trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene or 1, 4-phenylene.
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32Each independently preferably represents-CH2O-、-CF2O-、-CH2CH2-、-CF2CF2-or a single bond, further preferably-CH2O-、-CH2CH2-or a single bond, particularly preferably-CH2O-or a single bond.
XN21Fluorine atoms are preferred.
TN31Oxygen atoms are preferred.
nN11+nN12、nN21+nN22And nN31+nN32Preferably 1 or 2, preferably nN11Is 1 and nN12A combination of 0, nN11Is 2 and nN12A combination of 0, nN11Is 1 and nN12Is a combination of 1, nN11Is 2 and nN12Is a combination of 1, nN21Is 1 and nN22A combination of 0, nN21Is 2 and nN22A combination of 0, nN31Is 1 and nN32A combination of 0, nN31Is 2 and nN32Is a combination of 0.
The lower limit of the preferable content of the compound represented by the formula (N-1) is 1 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, and 80 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95 mass% or less, 85 mass% or less, 75 mass% or less, 65 mass% or less, 55 mass% or less, 45 mass% or less, 35 mass% or less, 25 mass% or less, or 20 mass% or less.
The lower limit of the preferable content of the compound represented by the formula (N-2) is 1 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, and 80 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95 mass% or less, 85 mass% or less, 75 mass% or less, 65 mass% or less, 55 mass% or less, 45 mass% or less, 35 mass% or less, 25 mass% or less, or 20 mass% or less.
The lower limit of the preferable content of the compound represented by the formula (N-3) is 1 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, and 80 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95 mass% or less, 85 mass% or less, 75 mass% or less, 65 mass% or less, 55 mass% or less, 45 mass% or less, 35 mass% or less, 25 mass% or less, or 20 mass% or less.
When a composition having a low viscosity and a high response speed is required for the liquid crystal composition of the present invention, the lower limit value and the upper limit value are preferably low. Further, when the Tni of the liquid crystal composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable that the lower limit value is low and the upper limit value is low. In addition, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value is high and the upper limit value is high.
The compounds represented by the general formula (N-1) include compounds represented by the following general formulae (N-1a) to (N-1 g).
[ solution 17]
(in the formula, RN11And RN12R in the general formula (N-1)N11And RN12Same meaning, nNa11Represents 0 or 1, nNb11Represents 1 or 2, nNc11Represents 0 or 1, nNe11Represents 1 or 2, nNg11Represents 1 or 2, ANe11Represents trans-1, 4-cyclohexylene or 1, 4-phenylene, ANg11To express contraryFormula-1, 4-cyclohexylene, 1, 4-cyclohexenylene or 1, 4-phenylene and at least 1 represents 1, 4-cyclohexenylene, ZNe11Represents a single bond or an ethylene group, at least 1 of which represents an ethylene group, and a plurality of A's present in the moleculeNe11、ZNe11And/or ANg11May be the same or different. )
More specifically, the compound represented by the general formula (N-1) is preferably a compound selected from the group of compounds represented by the general formulae (N-1-1) to (N-1-21).
The compound represented by the general formula (N-1-1) is the following compound.
[ solution 18]
(in the formula, RN111And RN112Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN111Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a propyl group, a pentyl group or a vinyl group. RN112Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group or a butoxy group.
The compounds represented by the general formula (N-1-1) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be less. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-1) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, 20 mass% or more, 23 mass% or more, 25 mass% or more, 27 mass% or more, 30 mass% or more, 33 mass% or more, or 35 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 50% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, and 3% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-1) is preferably a compound selected from the group consisting of compounds represented by the formulae (N-1-1.1) to (N-1-1.25), preferably compounds represented by the formulae (N-1-1.1) to (N-1-1.4), preferably compounds represented by the formulae (N-1-1.1) and (N-1-1.3).
[ solution 19]
The compounds represented by the formulae (N-1-1.1) to (N-1-1.25) may be used alone or in combination, and the lower limit of the preferable content of these compounds alone or in combination is 5% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass or more, 30% by mass or more, 33% by mass or more, or 35% by mass or more relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 50% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, and 3% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-2) is the following compound.
[ solution 20]
(in the formula, RN121And RN122Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN121Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group, a butyl group or a pentyl group. RN122Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, preferably a methyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group.
The compounds represented by the general formula (N-1-2) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When importance is attached to improvement of Δ ∈, it is preferable to set the content higher, when importance is attached to solubility at low temperature, it is more effective to set the content smaller, and when importance is attached to TNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-2) is 5 mass% or more, 7 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, 20 mass% or more, 23 mass% or more, 25 mass% or more, 27 mass% or more, 30 mass% or more, 33 mass% or more, 35 mass% or more, 37 mass% or more, 40 mass% or more, and 42 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 50% by mass or less, 48% by mass or less, 45% by mass or less, 43% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, and 5% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-2) is preferably a compound selected from the group consisting of the compounds represented by the formulae (N-1-2.1) to (N-1-2.25), preferably the compounds represented by the formulae (N-1-2.3) to (N-1-2.7), the formulae (N-1-2.10), (N-1-2.11), (N-1-2.13) and (N-1-2.20), and when an improvement in. DELTA.. epsilon.is important, the compounds represented by the formulae (N-1-2.3) to (N-1-2.7) are preferable, and T is importantNIThe compound represented by the formula (N-1-2.10), the formula (N-1-2.11) or the formula (N-1-2.13) is preferable for the improvement of (4), and the compound represented by the formula (N-1-2.20) is preferable for the improvement of the response speed.
[ solution 21]
The compounds represented by the formulae (N-1-2.1) to (N-1-2.25) may be used alone or in combination, and the lower limit of the preferable content of these compounds alone or in combination is 5% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass or more, 30% by mass or more, 33% by mass or more, or 35% by mass or more relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 50% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, and 3% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-3) is the following compound.
[ solution 22]
(in the formula, RN131And RN132Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN131Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. RN132Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, preferably a 1-propenyl group, an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-3) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-3) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-3) is preferably a compound selected from the group consisting of compounds represented by the formulae (N-1-3.1) to (N-1-3.21), preferably compounds represented by the formulae (N-1-3.1) to (N-1-3.7) and (N-1-3.21), preferably compounds represented by the formulae (N-1-3.1), (N-1-3.2), (N-1-3.3), (N-1-3.4) and (N-1-3.6).
[ solution 23]
The compounds represented by the formulae (N-1-3.1) to (N-1-3.4), (N-1-3.6) and (N-1-3.21) may be used alone or in combination, and preferably a combination of the formulae (N-1-3.1) and (N-1-3.2), a combination of 2 or 3 selected from the formulae (N-1-3.3), (N-1-3.4) and (N-1-3.6). The lower limit of the preferable content of these compounds alone or in combination is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-4) is the following compound.
[ solution 24]
(in the formula, RN141And RN142Each independently representAnd R in the general formula (N-1)N11And RN12The same meaning is used. )
RN141And RN142Each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably a methyl group, a propyl group, an ethoxy group or a butoxy group.
The compounds represented by the general formula (N-1-4) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be less. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-4) is 3 mass% or more, 5 mass% or more, 7 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 11% by mass or less, 10% by mass or less, and 8% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-4) is preferably a compound selected from the group consisting of compounds represented by the formulae (N-1-4.1) to (N-1-4.14), preferably compounds represented by the formulae (N-1-4.1) to (N-1-4.4), preferably compounds represented by the formulae (N-1-4.1), (N-1-4.2) and (N-1-4.4).
[ solution 25]
The compounds represented by the formulae (N-1-4.1) to (N-1-4.14) may be used alone or in combination, and the lower limit of the preferable content of these compounds alone or in combination is 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, or 20% by mass or more relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 11% by mass or less, 10% by mass or less, and 8% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-5) is the following compound.
[ solution 26]
(in the formula, RN151And RN152Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN151And RN152Each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
The compounds represented by the general formula (N-1-5) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When importance is attached to the improvement of Δ ∈, the content is preferably set higher, and when importance is attached to the improvement of Δ ∈When the solubility at low temperature is small, the effect is good, and when T is regarded as importantNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-5) is 5 mass% or more, 8 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-5) is preferably a compound selected from the group consisting of compounds represented by the formulae (N-1-5.1) to (N-1-5.6), preferably compounds represented by the formulae (N-1-5.1), (N-1-5.2) and (N-1-5.4).
[ solution 27]
The compounds represented by the formulae (N-1-5.1), (N-1-5.2) and (N-1-5.4) may be used alone or in combination, and the lower limit of the preferable content of these compounds alone or in combination is 5% by mass or more, 8% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, 20% by mass or more relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-12) is the following compound.
[ solution 28]
(in the formula, RN1121And RN1122Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN1121Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. RN1122Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-12) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-12) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-13) is the following compound.
[ solution 29]
(in the formula, RN1131And RN1132Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN1131Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. RN1132Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-13) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-13) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-14) is the following compound.
[ solution 30]
(in the formula, RN1141And RN1142Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN1141Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. RN1142Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-14) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The types of the compounds used are, for example, 1,2,3,4, 5 or more as one embodiment of the present embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-14) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-1-15) is the following compound.
[ solution 31]
(in the formula, RN1151And RN1152Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN1151Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. RN1152Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-15) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-15) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compounds represented by the general formula (N-1-16) are the following compounds.
[ solution 32]
(in the formula, RN1161And RN1162Each independently represents R in the general formula (N)N11And RN12The same meaning is used. )
RN1161Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. RN1162Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-16) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-16) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compounds represented by the general formula (N-1-17) are the following compounds.
[ solution 33]
(in the formula, RN1171And RN1172Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN1171Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. RN1172Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-17) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-17) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
The compounds represented by the general formula (N-1-18) are the following compounds.
[ chemical 34]
(in the formula, RN1181And RN1182Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN1181Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or a butyl group. RN1182Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-18) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-18) is 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, and 13% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
Further, the compound represented by the general formula (N-1-18) is preferably a compound selected from the group consisting of the compounds represented by the formulae (N-1-18.1) to (N-1-18.5), preferably a compound represented by the formulae (N-1-18.1) to (N-1-18.3), preferably a compound represented by the formulae (N-1-18.2) and (N-1-18.3).
[ solution 35]
The compound represented by the general formula (N-1-22) is the following compound.
[ solution 36]
(in the formula, RN1221And RN1222Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN1221And RN1222Each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.
The compounds represented by the general formula (N-1-22) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be more than a few. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-1-22) is 1 mass% or more, 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, or 5% by mass or less with respect to the total amount of the liquid crystal composition of the present invention.
Further, the compound represented by the general formula (N-1-22) is preferably a compound selected from the group of compounds represented by the formulae (N-1-22.1) to (N-1-22.12), preferably a compound represented by the formulae (N-1-22.1) to (N-1-22.5), preferably a compound represented by the formulae (N-1-22.1) to (N-1-22.4).
[ solution 37]
The compound represented by the general formula (N-3) is preferably a compound selected from the group of compounds represented by the general formulae (N-3-1) to (N-3-3), and among these, a compound selected from the group of compounds represented by the general formulae (N-3-1) and (N-3-2) is preferred, and a compound represented by the general formula (N-3-2) is preferred.
[ solution 38]
(in the formula, RN31And RN32Each independently represents R in the general formula (N-3)N31And RN32The same meaning is used. )
The compounds represented by the general formula (N-3-2) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1,2,3,4, 5 or more as one embodiment.
When the improvement of Δ ∈ is emphasized, it is preferable to set the content higher, when the solubility at low temperature is emphasized, it is more effective, and when T is emphasizedNIThe effect is good if the content is set to be less. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (N-3-2) is 3 mass% or more, 5 mass% or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, 20 mass% or more, 23 mass% or more, 25 mass% or more, 27 mass% or more, 30 mass% or more, 33 mass% or more, or 35 mass% or more with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 50 mass% or less, 40 mass% or less, 38 mass% or less, 35 mass% or less, 33 mass% or less, 30 mass% or less, 28 mass% or less, 25 mass% or less, 23 mass% or less, 20 mass% or less, 18 mass% or less, 15 mass% or less, 13 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, 6 mass% or less, and 5 mass% or less with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (N-3-2) is preferably a compound selected from the group of compounds represented by the formulae (N-3-2.1) to (N-3-2.3).
[ solution 39]
The polymerizable liquid crystal composition of the present invention preferably contains 1 or more compounds represented by the general formula (L).
[ solution 40]
(in the formula, wherein,
RL1and RL2Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent 2 or more-CH2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,
nL1represents 0, 1,2 or 3,
AL1、AL2and AL3Each independently represents a group selected from the group consisting of,
(a)1, 4-cyclohexylene (1-CH present in the radical)2-or 2 or more-CH not adjacent2-may be substituted by-O-. ) And
(b)1, 4-phenylene (1-CH-or nonadjacent 2 or more-CH-present in the radical may be substituted by-N)
(c) Naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or 2 or more-CH ═ which are not adjacent may be substituted by-N ═ can be used.)
The above-mentioned group (a), group (b) and group (c) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,
ZL1and ZL2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,
nL1is 2 or 3 or AL2When there are plural, they may be the same or different, and nL1Is 2 or 3 and thus ZL2When a plurality of them exist, they may be the same or different.
Wherein the compounds represented by the general formula (II) and the general formulae (N-1), (N-2) and (N-3) are excluded. )
The compound represented by the general formula (L) corresponds to a compound having a substantially neutral dielectric property (Δ ε has a value of-2 to 2). Therefore, the number of polar groups such as halogen contained in the molecule is preferably 2 or less, preferably 1 or less, and preferably no polar groups such as halogen are contained.
The compounds represented by the general formula (L) may be used alone or in combination. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with desired performances such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound used is, for example, 1 as one embodiment of the present invention. Or 2,3,4, 5, 6, 7, 8, 9, 10 or more in other embodiments of the present invention.
The content of the compound represented by the general formula (L) needs to be appropriately adjusted depending on the required performances such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like. The lower limit of the preferable content of the compound represented by the formula (L) is 1 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 75 mass%, 80 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of the compound represented by the formula (L) is 95 mass%, 85 mass%, 75 mass%, 65 mass%, 55 mass%, 45 mass%, 35 mass%, 25 mass%.
When the viscosity of the liquid crystal composition of the present invention is kept low and a liquid crystal composition having a high response speed is required, the lower limit value and the upper limit value of the content of the compound represented by the general formula (L) are preferably high. When the Tni of the liquid crystal composition of the present invention is kept high and a liquid crystal composition having good temperature stability is required, the lower limit value and the upper limit value of the content of the compound represented by the general formula (L) are preferably high. When the dielectric anisotropy is to be increased in order to keep the driving voltage low, the lower limit and the upper limit of the content of the compound represented by the general formula (L) are preferably set to be low.
With respect to RL1And RL2In order to place importance on reliability, both alkyl groups are preferred, in order to place importance on reduction of volatility of the compound, alkoxy groups are preferred, and in order to place importance on reduction of viscosity, at least one of the alkyl groups is preferably an alkenyl group.
With respect to RL1And RL2When the ring structure to which the compound is bonded is a phenyl group (aromatic group), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and an alkenyl group having 4 to 5 carbon atoms are preferable, and when the ring structure to which the compound is bonded is a saturated ring structure such as cyclohexane, pyran, dioxane, or the like, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms when present is preferably 5 or less, and is preferably linear.
The alkenyl group is preferably selected from groups represented by any one of the formulae (R1) to (R5). (Black dots in each formula represent carbon atoms in the ring structure.)
[ solution 41]
With respect to nL1When importance is attached to the response speed, 0 is preferable, 2 or 3 is preferable for improving the upper limit temperature of the nematic phase, and 1 is preferable for achieving the balance therebetween. In addition, in order to satisfy the characteristics required as a liquid crystal composition, it is preferable to combine compounds having different values.
With respect to AL1、AL2And AL3When Δ n is required to be increased, it is preferably aromatic, and it is preferably aliphatic for improving the response speed, and each independently preferably represents trans-1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] 2]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, more preferably represents the following structure, and still more preferably represents trans-1, 4-cyclohexylene or 1, 4-phenylene.
[ solution 42]
ZL1And ZL2When importance is attached to the response speed, a single bond is preferable.
In the compound represented by the general formula (L), the number of halogen atoms present in the molecule is preferably 0, 1,2 or 3, and preferably 0 or 1, and when importance is attached to compatibility with other liquid crystal molecules, it is preferably 1.
The polymerizable liquid crystal composition of the present invention particularly preferably contains 1 or more compounds represented by the following general formula (L-1A).
[ solution 43]
(in the above general formula (L-1A), RL11AAnd RL12AEach independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent 2 or more-CH2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-, RL11AAnd RL12A1 or non-adjacent 2 or more-CH in the alkyl group2Each independently may be substituted by-CH ═ CH-. )
With respect to the compound represented by the general formula (L-1A), RL11AAnd RL12AAt least one of them represents 1 or non-adjacent 2 or more-CH in the alkyl group2-each independently substituted with-CH ═ CH-. That is, in the compound represented by the general formula (L-1A), RL11AAnd RL12AAt least one of the above groups represents an alkenyl group having 2 to 8 carbon atoms.
The compound represented by the general formula (L-1A) has an alkenyl group, and therefore, the viscosity of the liquid crystal composition can be reduced, and a high-speed response can be achieved, and therefore, the response time can be shortened. In contrast, since the polymerizable liquid crystal composition of the present invention contains the polymerizable light stabilizer represented by the general formula (II), impurities generated by the photodegradation of the compound represented by the general formula (L-1A) are captured by the polymerizable light stabilizer, and thus the decrease in reliability and stability can be suppressed, and the content of the general formula (L-1A) can be increased to further reduce the viscosity and response speed. Thus, the polymerizable liquid crystal composition of the present invention exhibits high Δ ∈ and low viscosity, and can realize high-speed response and high stability.
Among these, RL11AAnd RL12AAt least one of the above is preferably represented by any one of the above-described formulae (R1) to (R5). In addition, RL11AAnd RL12AIn (3), only one may be an alkenyl group, or R may beL11AAnd RL12ABoth are alkenyl groups. RL11AAnd RL12AWhen both are alkenyl, RL11AAnd RL12AMay be the same or different.
RL11AAnd RL12AAt least one of them particularly preferably represents an alkenyl group having 2 to 5 carbon atoms.
The polymerizable liquid crystal composition of the present invention may contain at least 1 kind of compound represented by the general formula (L-1A), and 2 or more kinds may be contained in combination. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kinds of the compounds used are, for example, 1,2,3,4, 5 or more.
The lower limit of the total amount of the compound represented by the general formula (L-1A) is preferably 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 15 mass%, 20 mass%, 25 mass%, 30 mass%, 35 mass%, 40 mass%, 45 mass%, 50 mass%, and 55 mass% with respect to the total amount of the liquid crystal composition of the present invention. The preferable upper limit of the total amount is 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, and 25 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-1A) is preferably a compound selected from the group of compounds represented by the general formula (L-1A-1).
[ solution 44]
(in the formula, RL12ARepresents the same meaning as in the general formula (L-1A). )
The compound represented by the general formula (L-1A-1) is preferably a compound selected from the group consisting of compounds represented by the formulae (L-1A-1.1) to (L-1A-1.3), preferably a compound represented by the formula (L-1A-1.2) or (L-1A-1.3), and particularly preferably a compound represented by the formula (L-1A-1.3).
[ solution 45]
The lower limit of the preferable content of the compound represented by the formula (L-1A-1) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 20 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass% with respect to the total amount of the liquid crystal composition of the present invention. Among these, the compound represented by the formula (L-1A-3) is preferably contained within the range between the lower limit and the upper limit.
The compound represented by the general formula (L-1A) is preferably a compound selected from the group of compounds represented by the general formula (L-1A-2).
[ solution 46]
(in the formula, RL12ARepresents the same meaning as in the general formula (L-1A). )
The lower limit of the preferable content of the compound represented by the formula (L-1A-2) is 1 mass%, 5 mass%, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 60 mass%, 55 mass%, 50 mass%, 45 mass%, 42 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-1A-2) is preferably a compound selected from the group consisting of compounds represented by the formulae (L-1A-2.1) to (L-1A-2.4), and is preferably a compound represented by the formulae (L-1A-2.2) to (L-1A-2.4). In particular, the compound represented by the formula (L-1A-2.2) is preferable because it improves the response speed of the liquid crystal composition of the present invention. In addition, when higher Tni is required than the response speed, it is preferable to use a compound represented by the formula (L-1A-2.3) or the formula (L-1A-2.4). The content of the compound represented by the formula (L-1A-2.3) or the formula (L-1A-2.4) is not preferably 30% by mass or more in order to improve the solubility at low temperatures.
[ solution 47]
When the polymerizable liquid crystal composition of the present invention contains a compound represented by the formula (L-1A-2.2), the lower limit of the preferable content of the compound represented by the formula (L-1A-2.2) is 10 mass%, 15 mass%, 18 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 33 mass%, 35 mass%, 38 mass%, 40 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 60 mass%, 55 mass%, 50 mass%, 45 mass%, 43 mass%, 40 mass%, 38 mass%, 35 mass%, 32 mass%, 30 mass%, 27 mass%, 25 mass%, 22 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The polymerizable liquid crystal composition of the present invention preferably contains both the compound represented by the formula (L-1A-1.3) and the compound represented by the formula (L-1A-2.2). The lower limit value of the total preferable content of the compound represented by the formula (L-1A-1.3) and the compound represented by the formula (L-1A-2.2) is 10 mass%, 15 mass%, 20 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass%, 40 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 60 mass%, 55 mass%, 50 mass%, 45 mass%, 43 mass%, 40 mass%, 38 mass%, 35 mass%, 32 mass%, 30 mass%, 27 mass%, 25 mass%, 22 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-1A) is preferably a compound selected from the group consisting of compounds represented by the general formulae (L-1A-4) and (L-1A-5).
[ solution 48]
(in the formula, RL12ARepresents the same meaning as in the general formula (L-1A). )
In the general formulae (L-1A-4) and (L-1A-5), RL12AThe alkyl group having 1 to 8 carbon atoms, the alkoxy group having 1 to 8 carbon atoms or the alkenyl group having 2 to 8 carbon atoms is preferable, and the alkyl group having 1 to 5 carbon atoms is preferable to be linear, the alkoxy group having 1 to 4 carbon atoms is preferable to be linear, and the alkenyl group having 2 to 5 carbon atoms is preferable to be linear.
The lower limit of the preferable content of the compound represented by the formula (L-1A-4) is 1 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 25 mass%, 23 mass%, 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The lower limit of the preferable content of the compound represented by the formula (L-1A-5) is 1 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 25 mass%, 23 mass%, 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compounds represented by the general formulae (L-1A-4) and (L-1A-5) are preferably compounds selected from the group of compounds represented by the formulae (L-1A-4.1) to (L-1A-5.3), and are preferably compounds represented by the formula (L-1A-4.2) or the formula (L-1A-5.2).
[ solution 49]
When the polymerizable liquid crystal composition of the present invention contains a compound represented by the formula (L-1A-4.2), the lower limit of the preferable content of the compound represented by the formula (L-1A-4.2) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 13 mass%, 15 mass%, 18 mass%, or 20 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-1A) is preferably a compound selected from the group of compounds represented by the general formula (L-1A-6).
[ solution 50]
(in the formula, RL17And RL18Each independently represents a methyl group or a hydrogen atom. )
The lower limit of the preferable content of the compound represented by the formula (L-1A-6) is 1 mass%, 5 mass%, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 60 mass%, 55 mass%, 50 mass%, 45 mass%, 42 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-1A-6) is preferably a compound selected from the group consisting of compounds represented by the formulae (L-1A-6.1) to (L-1A-6.3).
[ solution 51]
In addition, in the polymerizable liquid crystal composition of the present invention, it is preferable that the compound represented by the general formula (L) further contains 1 or 2 or more compounds selected from the group consisting of the compounds represented by the general formula (L-1B) and the compounds represented by the general formulae (L-2) to (L-7) in addition to the compound represented by the general formula (L-1A).
The compound represented by the general formula (L-1B) is the following compound.
[ solution 52]
(in the formula, RL11BAnd RL12BEach independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent 2 or more-CH2-each independently may be substituted by-C.ident.C-, -O-, -CO-, -COO-or-OCO-. )
A compound represented by the general formula (L-1B) in RL11BAnd RL12BOne or both of them do not represent an alkenyl group, and is different from the compound represented by the general formula (L-1A).
RL11BAnd RL12BPreferably a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms.
The polymerizable liquid crystal composition of the present invention may contain 1 kind of the compound represented by the general formula (L-1B), or may contain 2 or more kinds in combination. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kinds of the compounds used are, for example, 1,2,3,4, 5 or more.
The lower limit of the preferable content of the compound represented by the formula (L-1B) is 1 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 30 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 37 mass%, 35 mass%, 33 mass%, 30 mass%, 27 mass%, 25 mass%, 23 mass%, 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-1B) is preferably a compound selected from the group of compounds represented by the formulae (L-1B-1) to (L-1B-13), and is preferably a compound selected from the group of compounds represented by the formulae (L-1B-1), (L-1B-3) and (L-1B-4). In particular, the compound represented by the formula (L-1B-1) is preferable because it improves the response speed of the liquid crystal composition of the present invention. In addition, when higher Tni is required than the response speed, it is preferable to use a compound selected from the group of compounds represented by the formula (L-1B-3), the formula (L-B-4), the formula (L-B-11) and the formula (L-1B-12). In order to improve the solubility at low temperatures, the total content of the compounds represented by the formulae (L-1B-3), (L-1B-4), (L-1B-11) and (L-1B-13) is not preferably 20% by mass or more.
[ Hua 53]
When the liquid crystal composition of the present invention contains the compound represented by the formula (L-1B-1), the lower limit of the preferable content of the compound represented by the formula (L-1B-1) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 13 mass%, 15 mass%, 18 mass%, 20 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The polymerizable liquid crystal composition of the present invention preferably contains 2 or more compounds selected from the group of compounds represented by the formula (L-1A-1.3), the formula (L-1A-2.2), the formula (L-1B-1), the formula (L-1B-3), the formula (L-1B-4), the formula (L-1B-11) and the formula (L-1B-12) in combination. The polymerizable liquid crystal composition of the present invention preferably contains 2 or more compounds selected from the group consisting of the compounds represented by the formulae (L-1A-1.3), (L-1A-2.2), (L-1B-1), (L-1B-3), (L-B-4) and (L-1A-4.2). The preferable lower limit of the total content of these compounds is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 13 mass%, 15 mass%, 18 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 33 mass%, 35 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 80 mass%, 70 mass%, 60 mass%, 50 mass%, 45 mass%, 40 mass%, 37 mass%, 35 mass%, 33 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass% with respect to the total amount of the liquid crystal composition of the present invention.
When importance is attached to the reliability of the liquid crystal composition, it is preferable to combine 2 or more compounds selected from the group consisting of the compounds represented by the formulae (L-1B-1), (L-1B-3) and (L-1B-4). When importance is attached to the response speed of the liquid crystal composition, it is preferable to combine 2 or more compounds selected from the group consisting of the compounds represented by the formula (L-1A-1.3) and the formula (L-1A-2.2).
The polymerizable liquid crystal composition of the present invention preferably contains 1 or more compounds represented by the general formula (L-1A) and 1 or more compounds represented by the general formula (L-1B). The preferable lower limit value of the total amount of the compound represented by the general formula (L-1A) and the compound represented by the general formula (L-1B) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 15 mass%, 20 mass%, 25 mass%, 30 mass%, 35 mass%, 40 mass%, 45 mass%, 50 mass%, and 55 mass% with respect to the total amount of the liquid crystal composition of the present invention. The preferable upper limit of the content is 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass% with respect to the total amount of the liquid crystal composition of the present invention.
When the viscosity of the liquid crystal composition of the present invention is kept low and a composition having a high response speed is required, it is preferable that the lower limit value and the upper limit value of the total amount of the compound represented by the general formula (L-1A) and the compound represented by the general formula (L-1B) are high. When the Tni of the liquid crystal composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable that the lower limit value and the upper limit value of the total amount of the compound represented by the general formula (L-1A) and the compound represented by the general formula (L-1B) are centered. In addition, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value and the upper limit value of the total amount of the compound represented by the general formula (L-1A) and the compound represented by the general formula (L-1B) are low.
The compound represented by the general formula (L-2) is the following compound.
[ solution 54]
(in the formula, RL21And RL22Each independently represents R in the general formula (L)L1And RL2The same meaning is used. )
RL21Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. In addition, RL22Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an unsaturated bond of the alkenyl group is not directly bonded to benzene.
The compounds represented by the general formula (L-2) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1 kind, 2 kinds, 3 kinds, 4 kinds, 5 kinds or more as one embodiment of the present invention.
When the solubility at low temperature is regarded as important, the effect is good if the content is set to be higher, whereas when the response speed is regarded as important, the effect is good if the content is set to be lower. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The lower limit of the preferable content of the compound represented by the formula (L-2) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 20 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-2) is preferably a compound selected from the group consisting of compounds represented by the formulae (L-2.1) to (L-2.6), and is preferably a compound represented by the formulae (L-2.1), (L-2.3), (L-2.4) and (L-2.6).
[ solution 55]
The compound represented by the general formula (L-3) is the following compound.
[ solution 56]
(in the formula, RL31And RL32Each independently represents R in the general formula (L)L1And RL2The same meaning is used. )
RL31And RL32Each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Further, it is preferable that the unsaturated bond of the alkenyl group is not directly bonded to benzene.
The compounds represented by the general formula (L-3) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1 kind, 2 kinds, 3 kinds, 4 kinds, 5 kinds or more as one embodiment of the present invention.
The lower limit of the preferable content of the compound represented by the formula (L-3) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 20 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass% with respect to the total amount of the liquid crystal composition of the present invention.
When a high birefringence is to be obtained, it is effective to set the content higher, whereas when high Tni is regarded as important, it is effective to set the content lower. Further, when the dropping mark and the burn-in characteristic are improved, it is preferable to set the range of the content to be centered.
The compound represented by the general formula (L-3) is preferably a compound selected from the group of compounds represented by the formulae (L-3.1) to (L-3.7), and is preferably a compound represented by the formulae (L-3.2) to (L-3.5).
[ solution 57]
The compound represented by the general formula (L-4) is the following compound.
[ solution 58]
(in the formula, RL41And RL42Each independently represents R in the general formula (L)L1And RL2The same meaning is used. )
RL41Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, RL42Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Preferably, the unsaturated bond of the alkenyl group is not directly connected to benzene.
The compounds represented by the general formula (L-4) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1 kind, 2 kinds, 3 kinds, 4 kinds, 5 kinds or more as one embodiment of the present invention.
In the liquid crystal composition of the present invention, the content of the compound represented by the general formula (L-4) needs to be appropriately adjusted depending on the required performances such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like.
The lower limit of the preferable content of the compound represented by the formula (L-4) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, 20 mass%, 23 mass%, 26 mass%, 30 mass%, 35 mass%, 40 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of the compound represented by the formula (L-4) is 50 mass%, 40 mass%, 35 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compounds represented by the general formula (L-4) are preferably, for example, compounds represented by the formulae (L-4.1) to (L-4.3).
[ chemical 59]
The compound represented by the formula (L-4.1), the compound represented by the formula (L-4.2), both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2), or all of the compounds represented by the formulae (L-4.1) to (L-4.3) may be contained in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The lower limit of the preferable content of the compound represented by the formula (L-4.1) or the formula (L-4.2) is 3 mass%, 5 mass%, 7 mass%, 9 mass%, 11 mass%, 12 mass%, 13 mass%, 18 mass%, 21 mass%, and the upper limit thereof is 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass% with respect to the total amount of the liquid crystal composition of the present invention.
When both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) are contained, the lower limit of the preferable content of both compounds is 15 mass%, 19 mass%, 24 mass%, 30 mass%, and the upper limit thereof is 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-4) is preferably a compound represented by the formula (L-4.4) to the formula (L-4.6), and is preferably a compound represented by the formula (L-4.4).
[ solution 60]
The compound represented by the formula (L-4.4), the compound represented by the formula (L-4.5), or both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) may be contained in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like.
The lower limit of the preferable content of the compound represented by the formula (L-4.4) or the formula (L-4.5) is 3 mass%, 5 mass%, 7 mass%, 9 mass%, 11 mass%, 12 mass%, 13 mass%, 18 mass%, 21 mass% with respect to the total amount of the liquid crystal composition of the present invention. The preferable upper limit is 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%.
When both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) are contained, the lower limit of the preferable content of both compounds is 15 mass%, 19 mass%, 24 mass%, 30 mass%, and the upper limit thereof is 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-4) is preferably a compound represented by the formulae (L-4.7) to (L-4.10), and particularly preferably a compound represented by the formula (L-4.9).
[ solution 61]
The compound represented by the general formula (L-5) is the following compound.
[ solution 62]
(in the formula, RL51And RL52Each independently represents R in the general formula (L)L1And RL2The same meaning is used. )
RL51Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, RL52Preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Preferably, the unsaturated bond of the alkenyl group is not directly connected to benzene.
The compounds represented by the general formula (L-5) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1 kind, 2 kinds, 3 kinds, 4 kinds, 5 kinds or more as one embodiment of the present invention.
In the liquid crystal composition of the present invention, the content of the compound represented by the general formula (L-5) needs to be appropriately adjusted depending on the required performances such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like.
The lower limit of the preferable content of the compound represented by the formula (L-5) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, 20 mass%, 23 mass%, 26 mass%, 30 mass%, 35 mass%, 40 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of the compound represented by the formula (L-5) is 50 mass%, 40 mass%, 35 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass% with respect to the total amount of the liquid crystal composition of the present invention.
The compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.1) or the formula (L-5.2), and particularly preferably a compound represented by the formula (L-5.1).
[ solution 63]
The lower limit of the preferable content of these compounds is 1 mass%, 2 mass%, 3 mass%, 5 mass%, and 7 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of these compounds is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 9 mass%.
The compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.3) or the formula (L-5.4).
[ solution 64]
The lower limit of the preferable content of these compounds is 1 mass%, 2 mass%, 3 mass%, 5 mass%, and 7 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of these compounds is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 9 mass%.
The compound represented by the general formula (L-5) is preferably a compound selected from the group consisting of compounds represented by the formulae (L-5.5) to (L-5.7), and particularly preferably a compound represented by the formula (L-5.7).
[ solution 65]
The lower limit of the preferable content of these compounds is 1 mass%, 2 mass%, 3 mass%, 5 mass%, and 7 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of these compounds is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 9 mass%.
The compound represented by the general formula (L-6) is the following compound.
[ solution 66]
(in the formula, RL61And RL62Each independently represents R in the general formula (L)L1And RL2Same meaning as XL61And XL62Each independently represents a hydrogen atom or a fluorine atom. Wherein the compound represented by the general formula (N-1) is excluded. )
RL61And RL62Each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Preferably, the unsaturated bond of the alkenyl group is not directly connected to benzene.
XL61And XL62Preferably, one is a fluorine atom and the other is a hydrogen atom.
The compounds represented by the general formula (L-6) may be used alone or in combination of 2 or more. The kind of the compound that can be combined is not particularly limited, and it is suitably combined and used in accordance with the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound to be used is, for example, 1 kind, 2 kinds, 3 kinds, 4 kinds, 5 kinds or more as one embodiment of the present invention.
The lower limit of the preferable content of the compound represented by the formula (L-6) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, 20 mass%, 23 mass%, 26 mass%, 30 mass%, 35 mass%, 40 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of the compound represented by the formula (L-6) is 50 mass%, 40 mass%, 35 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass% with respect to the total amount of the liquid crystal composition of the present invention. When the emphasis is placed on increasing Δ n, the content is preferably increased, and when the emphasis is placed on precipitation at a low temperature, the content is preferably decreased.
The compound represented by the general formula (L-6) is preferably a compound represented by the formula (L-6.1) to the formula (L-6.9).
[ solution 67]
The kind of the compound which can be combined is not particularly limited, and the compound preferably contains 1 to 3 kinds, and more preferably contains 1 to 4 kinds. Further, since the wide molecular weight distribution of the selected compound is effective also for solubility, it is preferable to select 1 from the compounds represented by the formula (L-6.1) or (L-6.2), 1 from the compounds represented by the formula (L-6.4) or (L-6.5), 1 from the compounds represented by the formula (L-6.6) or (L-6.7), 1 from the compounds represented by the formula (L-6.8) or (L-6.9), and appropriately combine them. Among them, preferred are compounds represented by the formula (L-6.1), the formula (L-6.3), the formula (L-6.4), the formula (L-6.6) and the formula (L-6.9).
The compound represented by the general formula (L-6) is preferably, for example, a compound represented by the formula (L-6.10) to the formula (L-6.17), and among them, a compound represented by the formula (L-6.11) is preferable.
[ solution 68]
The lower limit of the preferable content of these compounds is 1 mass%, 2 mass%, 3 mass%, 5 mass%, and 7 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of these compounds is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 9 mass%.
The compound represented by the general formula (L-7) is the following compound.
[ solution 69]
(in the formula, RL71And RL72Each independently represents R in the general formula (L)L1And RL2Same meaning as AL71And AL72Each independently represents a group represented by the general formula (L)L2And AL3Same meaning as AL71And AL72Each hydrogen atom in (A) may independently be substituted by a fluorine atom, ZL71Is represented by Z in the general formula (L)L2Same meaning as XL71And XL72Each independently represents a fluorine atom or a hydrogen atom. Wherein compounds represented by the general formula (II) and compounds represented by the general formulae (N-1) to (N-3) are excluded. )
In the formula, RL71And RL72Each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Preferably, the unsaturated bond of the alkenyl group is not directly connected to benzene.
AL71And AL72Each independently of the others preferably being 1, 4-cyclohexylene or 1, 4-phenylene, AL71And AL72Each hydrogen atom may independently be replaced by a fluorine atom,
ZL71preferably a single bond or-COO-, preferably a single bond.
XL71And XL72Preferably both are hydrogen atoms.
The kind of the compound that can be combined is not particularly limited, and the compound is combined according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The types of the compounds used are, for example, 1,2,3, and 4 as one embodiment of the present invention.
In the liquid crystal composition of the present invention, the content of the compound represented by the general formula (L-7) needs to be appropriately adjusted depending on the required performances such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like.
The lower limit of the preferable content of the compound represented by the formula (L-7) is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, 20 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content of the compound represented by the formula (L-7) is 30 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 10 mass%, 5 mass% with respect to the total amount of the liquid crystal composition of the present invention.
When the liquid crystal composition of the present invention is expected to be an embodiment having a high Tni, the content of the compound represented by the formula (L-7) is preferably increased to some extent, and when the liquid crystal composition is expected to be an embodiment having a low viscosity, the content is preferably decreased to some extent.
The compound represented by the general formula (L-7) is preferably a compound represented by the formulae (L-7.1) to (L-7.4), and is preferably a compound represented by the formula (L-7.2).
[ solution 70]
The compound represented by the general formula (L-7) is preferably a compound represented by the formulae (L-7.11) to (L-7.13), preferably a compound represented by the formula (L-7.11).
[ solution 71]
The compounds represented by the general formula (L-7) are represented by the formulae (L-7.21) to (L-7.23). Preferred is a compound represented by the formula (L-7.21).
[ chemical formula 72]
The compound represented by the general formula (L-7) is preferably a compound represented by the formulae (L-7.31) to (L-7.34), preferably a compound represented by the formula (L-7.31) or/and (L-7.32).
[ solution 73]
The compound represented by the general formula (L-7) is preferably a compound represented by the formulae (L-7.41) to (L-7.44), preferably a compound represented by the formula (L-7.41) or/and (L-7.42).
[ chemical formula 74]
The compound represented by the general formula (L-7) is preferably a compound represented by the formulae (L-7.51) to (L-7.53).
[ solution 75]
In the liquid crystal composition of the present invention, the preferable lower limit value of the total content of the light stabilizer represented by the general formula (H), the liquid crystal compound represented by the general formula (II), the compound selected from the group of compounds represented by the general formulae (N-1) to (N-3), and the compound represented by the general formula (L) is 80 mass%, 85 mass%, 88 mass%, 90 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass%, 97 mass%, 98 mass%, 99 mass%, 100 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the total content is preferably 100 mass%, 99 mass%, 98 mass%, or 95 mass% of the total amount of the liquid crystal composition of the present invention.
In the liquid crystal composition of the present invention, the lower limit of the total content of the compound selected from the group of compounds represented by the general formula (II-1) and the compound represented by the general formula (L-1A) is preferably 1 mass%, 5 mass%, 10 mass%, 15 mass%, 20 mass%, 25 mass%, 30 mass%, 35 mass%, or 40 mass% based on the total amount of the liquid crystal composition of the present invention. The upper limit of the total content is preferably 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 45 mass%, and 30 mass% of the total amount of the liquid crystal composition of the present invention.
(other additives)
The polymerizable liquid crystal composition of the present invention preferably contains 1 or more compounds selected from the group consisting of an antioxidant, an ultraviolet absorber, and a polymerization initiator. The compound selected from the group consisting of an antioxidant, an ultraviolet absorber, and a polymerization initiator is referred to as "other additive". This is because the polymerizable liquid crystal composition of the present invention can improve the reliability of the liquid crystal composition by using 1 or more compounds selected from the group consisting of an antioxidant, an ultraviolet absorber, and a polymerization initiator in addition to the light stabilizer represented by the general formula (H), and by utilizing the synergy between the effects of the light stabilizer represented by the general formula (H) and the effects of the other additives described below.
The polymerizable liquid crystal composition of the present invention preferably contains 1 or more antioxidants. By using an antioxidant in addition to the light stabilizer represented by the general formula (H), the impurities generated can be made harmless. The antioxidant may be a known antioxidant used in liquid crystal compositions, and among these, a hindered phenol antioxidant is preferable. This is because, in the hindered phenol antioxidant, a hydroxyl group is adjacent to an alkyl group having a large steric hindrance, and therefore, the hindered phenol antioxidant is not easily deactivated, and can sufficiently exhibit the function of the antioxidant. The hindered phenol-based antioxidant is an antioxidant having a hindered phenol skeleton.
The content of the antioxidant is preferably 0.0001% by mass or more, 0.005% by mass or more, and 0.01% by mass or more relative to the total amount of the liquid crystal composition of the present invention, and the content is preferably 0.1% by mass or less, 0.05% by mass or less, and 0.03% by mass or less. If the content of the antioxidant is too large and exceeds the above range, the image quality of the panel may be deteriorated due to the deposition of the antioxidant, and if it is too small, the reliability of the liquid crystal composition may not be sufficiently improved.
The polymerizable liquid crystal composition of the present invention preferably contains 1 or more kinds of ultraviolet absorbers. By using an ultraviolet absorber in combination with the light stabilizer represented by the general formula (H), the amount of ultraviolet rays received by the liquid crystal composition can be reduced, and the photodegradation of the liquid crystal composition can be suppressed. Examples of the ultraviolet absorber include hydroxybenzophenone-based ultraviolet absorbers, hydroxyphenyl benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and salicylate-based ultraviolet absorbers. Among these, the polymerizable liquid crystal composition of the present invention preferably contains 1 or more types of ultraviolet absorbers containing no heteroatom other than oxygen, and more preferably contains 1 or more types of benzophenone-based ultraviolet absorbers, from the viewpoint of suppressing a decrease in reliability. This is because benzophenone-based ultraviolet absorbers have a smaller number of unpaired electrons in the molecule than other ultraviolet absorbers, and therefore, the purity is easily maintained and the reliability is easily improved. Specific examples of the benzophenone-based ultraviolet absorber include [ 2-hydroxy-4- (octyloxy) phenyl ] (phenyl) methanone (product name: manufactured by ADK STAB1413 ADEKA).
The content of the ultraviolet absorber is preferably 0.0001% by mass or more, 0.001% by mass or more, and 0.01% by mass or more, and is preferably 0.1% by mass or less, 0.05% by mass or less, and 0.02% by mass or less, based on the total amount of the liquid crystal composition of the present invention. If the content of the ultraviolet absorber is too large, the ultraviolet absorber may precipitate in the liquid crystal panel to cause a display failure of the liquid crystal panel, while if it is too small, the amount of ultraviolet rays to which the liquid crystal molecules are exposed may not be sufficiently reduced, and reliability may not be ensured.
The polymerizable liquid crystal composition of the present invention preferably contains 1 or more kinds of polymerizable initiators. By using the light stabilizer represented by the general formula (H) in combination with a polymerization initiator, the polymerization reaction of the polymerizable compound can be promoted, and a strong polymer layer composed of a polymer of the polymerizable compound is formed at the interface between the liquid crystal and the substrate, so that the insulating property of the liquid crystal cell is enhanced, and VHR can be improved.
The polymerizable initiator may be selected from known polymerizable initiators used in liquid crystal compositions, and examples thereof include benzoin ether type polymerizable initiators, benzophenone type polymerizable initiators, acetophenone type polymerizable initiators, benzil ketal type polymerizable initiators, acylphosphine oxide type polymerizable initiators, and the like. Of these, benzil ketal polymerization initiators are preferred. This is because the benzil ketal polymerization initiator has high photoreaction efficiency and can form a dense polymer layer. Specific examples of the benzil ketal polymerization initiator include 2, 2-dimethoxy-2-phenylacetophenone (product name: Irgacure 651).
The content of the polymerization initiator is preferably 0.0001% by mass or more and 0.001% by mass or more, and is preferably 0.005% by mass or less and 0.002% by mass or less, based on the total amount of the liquid crystal composition of the present invention. If the content of the polymerization initiator is too large and exceeds the above range, VHR may be reduced due to the influence of impurities contained in the polymerization initiator, and if it is too small, the polymerization may not be efficiently performed, the insulating property of the liquid crystal cell may not be improved, and VHR may not be improved.
The total amount of the compound selected from the group consisting of an antioxidant, an ultraviolet absorber, and a polymerization initiator is preferably 0.0001% by mass or more, 0.0005% by mass or more, 0.001% by mass or more, 0.005% by mass or more, and 0.01% by mass or more, and further preferably 0.2% by mass or less, 0.15% by mass or less, 0.1% by mass or less, and 0.05% by mass or less, relative to the total amount of the liquid crystal composition of the present invention.
The total amount of the compound represented by the general formula (H) and 1 or more compounds selected from the group consisting of an ultraviolet absorber, an antioxidant and a polymerization initiator is preferably 0.0011% by mass or more, 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, or 0.05% by mass or more, and further preferably 0.2% by mass or less, 0.15% by mass or less, 0.1% by mass or less, or 0.05% by mass or less, relative to the total amount of the liquid crystal composition of the present invention.
The preferable range of the total amount of the compound represented by the general formula (H) and 1 or more compounds selected from the group consisting of an ultraviolet absorber, an antioxidant and a polymerization initiator may be appropriately set in combination of the upper limit value and the lower limit value, and among these, the preferable range is 0.005 mass% to 0.2 mass%, 0.01 mass% to 0.2 mass%, and 0.01 mass% to 0.05 mass% with respect to the total amount of the liquid crystal composition of the present invention. By setting the total amount of the compound represented by the general formula (H) and the other additives to the above range, it is possible to introduce an additive sufficient for improving reliability into the liquid crystal composition, and also to suppress precipitation occurring when an excessive amount of the additive is introduced into the composition, thereby maintaining display quality.
(others)
The liquid crystal composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms are linked to each other, such as a peracid (-CO-OO-) structure, in the molecule.
When importance is attached to the reliability and long-term stability of the liquid crystal composition, the content of the compound having a carbonyl group is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and most preferably substantially none, based on the total amount of the liquid crystal composition.
When importance is attached to the stability by UV irradiation, the content of the compound substituted with a chlorine atom is preferably 15% by mass or less, preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, preferably 3% by mass or less, and further preferably substantially not contained, with respect to the total amount of the liquid crystal composition of the present invention.
The content of the compound having all ring structures in the molecule of a 6-membered ring is preferably increased, and the content of the compound having all ring structures in the molecule of a 6-membered ring is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and most preferably the liquid crystal composition of the present invention is constituted substantially only by the compound having all ring structures in the molecule of a 6-membered ring, based on the total amount of the liquid crystal composition of the present invention.
In order to suppress deterioration due to oxidation of the liquid crystal composition, the content of the compound having a cyclohexenylene group as a ring structure is preferably reduced, and the content of the compound having a cyclohexenylene group is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, preferably 3% by mass or less, and further preferably substantially not contained, relative to the total amount of the liquid crystal composition of the present invention.
When importance is attached to the improvement of viscosity and the improvement of Tni, the content of the compound having 2-methylbenzene-1, 4-diyl in which a hydrogen atom is substituted with halogen in the molecule is preferably reduced, and the content of the compound having 2-methylbenzene-1, 4-diyl in the molecule is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, preferably 3% by mass or less, and further preferably substantially none, relative to the total amount of the liquid crystal composition of the present invention.
The term "substantially free" in the present specification means not containing other than an unintentional substance (inevitable impurity).
The refractive index anisotropy (. DELTA.n) of the liquid crystal composition of the present invention at 20 ℃ is preferably in the range of 0.08 to 0.14, more preferably in the range of 0.09 to 0.13, and particularly preferably in the range of 0.09 to 0.12. In further detail, it is preferably in the range of 0.10 to 0.13 when corresponding to a thin cell gap, and in the range of 0.08 to 0.10 when corresponding to a thick cell gap.
The viscosity (. eta.) at 20 ℃ of the liquid crystal composition of the present invention is 10 to 50 mPas, more preferably 10 to 40 mPas, and particularly preferably 10 to 35 mPas.
Rotational viscosity at 20 ℃ of the liquid Crystal composition of the present invention (. gamma.)1) Preferably in the range of from 60 to 130 mPas, more preferably in the range of from 60 to 110 mPas, particularly preferably in the range of from 60 to 100 mPas.
Nematic phase-isotropic liquid phase transition temperature (T) of liquid crystal composition of the present inventionni) Preferably in the range of 60 ℃ to 120 ℃, more preferably in the range of 70 ℃ to 100 ℃, and particularly preferably in the range of 70 ℃ to 85 ℃.
(polymerizable Compound)
The polymerizable liquid crystal composition of the present invention contains 1 or more polymerizable compounds having 1 or more polymerizable groups in 1 molecule. The polymerizable compound is a compound that can be polymerized by irradiation with an active energy ray, and can form a pretilt angle of liquid crystal molecules appropriately.
The polymerizable compound may be a known polymerizable compound used in a liquid crystal composition, and among these, a compound represented by the following general formula (P) is preferable.
[ 76]
(in the above general formula (P), Rp1Represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or-Spp2-Pp21 or non-adjacent 2 or more-CH groups in the alkyl group2-each independently may be substituted by-CH- ═ CH-, -C.ident.C-, -O-, -CO-, -COO-or-OCO-, and 1 or more than 2 hydrogen atoms in the alkyl group may each independently be substituted by cyano groups, fluorine atoms or chlorine atoms,
Pp1and Pp2Each independently represents a general formula (P)p1-1) to formula (P)p1-any one of the above-mentioned-9),
[ solution 77]
(in the formula, Rp11And Rp12Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms, Wp11Represents a single bond, -O-, -COO-or methylene, tp11Represents a number of 0, 1 or 2,in the molecule of Rp11、Rp12、Wp11And/or tp11When a plurality of them exist, they may be the same or different. )
Spp1And Spp2Each independently represents a single bond or a spacer,
Zp1and Zp2Each independently represents a single bond, -O-, -S-, -CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRZP1-、-NRZP1-CO-、-SCH2-、-CH2S-、-CH＝CRZP1-COO-、-CH＝CRZP1-OCO-、-COO-CRZP1＝CH-、-OCO-CRZP1＝CH-、-COO-CRZP1＝CH-COO-、-COO-CRZP1＝CH-OCO-、-OCO-CRZP1＝CH-COO-、-OCO-CRZP1＝CH-OCO-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-(C＝O)-O-(CH2)2-、-CH＝CH-、-CF＝CF-、-CF＝CH-、-CH＝CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-or-C ≡ C- (wherein, R isZP1Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R in the moleculeZP1When a plurality of them exist, they may be the same or different. ),
Ap1、Ap2and Ap3Each independently represents a group selected from the group consisting of,
(ap)1, 4-cyclohexylene (1-CH present in the radical)2-or 2 or more-CH not adjacent2-may be substituted by-O-. )
(bp)1, 4-phenylene (1-CH ═ or nonadjacent 2 or more-CH ═ present in the group can be substituted by-N ═ or. ) And
(cp) Naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, phenanthrene-2, 7-diyl orAnthracene-2, 6-diyl (1-CH or 2 or more-CH which are not adjacent to each other may be substituted by-N, and a hydrogen atom present in the group may be substituted by a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 1 to 8 carbon atoms.)
The above group (a)p) Group (b)p) And a group (c)p) Wherein 1 or 2 or more hydrogen atoms present in the group (a) are independently a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms or-Spp2-Pp2Substituted, 1 or non-adjacent 2 or more-CH in the alkyl group2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,
mp1represents 0, 1,2 or 3, and Z is in the moleculep1、Ap2、Spp2And/or Pp2When plural, they may be the same or different, in mp1Is 0 and Ap1When it is phenanthrene-2, 7-diyl or anthracene-2, 6-diyl, Ap3Represents a single bond. )
Wherein the compound represented by the general formula (H) is excluded. )
The polymerizable liquid crystal composition of the present invention preferably contains 1 or 2 or more kinds of polymerizable compounds represented by the general formula (P).
In the general formula (P), Rp1Is preferably-Spp2-Pp2。
In the general formula (P), Pp1And Pp2Are each independently preferably of the formula (P)p1-1) to formula (P)p1-3), preferably (P)p1-1)。
In the general formula (P), Rp11And Rp12Each independently preferably a hydrogen atom or a methyl group.
In the general formula (P), tp11Preferably 0 or 1.
In the general formula (P), Wp11Preferably a single bond, methylene or ethylene.
In the general formula (P), mp1Preferably 0, 1 or 2, preferably 0 or 1.
In the general formula (P), Zp1And Zp2Each independently preferably being a single bond, -OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CH＝CH-、-CF2-、-CF2O-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-CH＝CH-COO-、-COO-CH＝CH-、-OCOCH＝CH-、-COO-(CH2)2-、-OCF2-or-C ≡ C-, preferably a single bond, -OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CH＝CH-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-CH＝CH-COO-、-COO-CH＝CH-、-OCOCH＝CH-、-COO-(CH2)2-or-C.ident.C-, preferably only 1 present in the molecule is-OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CH＝CH-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-CH＝CH-COO-、-COO-CH＝CH-、-OCOCH＝CH-、-COO-(CH2)2-or-C.ident.C-and all others are single bonds, preferably only 1 present in the molecule is-OCH2-、-CH2O-、-C2H4-, -COO-or-OCO-and the others are all single bonds, preferably all single bonds.
In addition, Z present in the molecule is preferablep1And Zp2Is selected from the group consisting of-CH-COO-, -COO-CH-, - (CH)2)2-COO-、-(CH2)2-OCO-、-O-CO-(CH2)2-、-COO-(CH2)2-a linker group and others of the group consisting of a single bond.
In the general formula (P), Spp1And Spp2Each independently represents a single bondOr a spacer, the spacer is preferably an alkylene group having 1 to 30 carbon atoms, in which-CH is present2The alkylene group may be substituted with-O-, -CO-, -COO-, -OCO-, -CH-or-C.ident.C-so that oxygen atoms are not directly bonded to each other, and a hydrogen atom in the alkylene group may be substituted with a halogen atom, and is preferably a linear alkylene group having 1 to 10 carbon atoms or a single bond.
In the general formula (P), Ap1、Ap2And Ap3Independently of one another, 1, 4-phenylene or 1, 4-cyclohexylene is preferred, 1, 4-phenylene being preferred. In order to improve the compatibility with the liquid crystal compound, the 1, 4-phenylene group is preferably substituted with 1 fluorine atom, 1 methyl group or 1 methoxy group.
The content of the compound represented by the general formula (P) is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, even more preferably 0.1 to 5% by mass, even more preferably 0.1 to 3% by mass, even more preferably 0.2 to 2% by mass, even more preferably 0.2 to 1.3% by mass, particularly preferably 0.2 to 1% by mass, and most preferably 0.2 to 0.56% by mass, based on the total amount of the polymerizable liquid crystal composition of the present invention.
The lower limit of the total content of the compounds represented by the general formula (P) is preferably 0.01 mass%, 0.03 mass%, 0.05 mass%, 0.08 mass%, 0.1 mass%, 0.15 mass%, 0.2 mass%, 0.25 mass%, 0.3 mass% with respect to the total amount of the polymerizable liquid crystal composition of the present invention. The upper limit of the total content of the compounds represented by the general formula (P) is preferably 10 mass%, 8 mass%, 5 mass%, 3 mass%, 1.5 mass%, 1.2 mass%, 1 mass%, 0.8 mass%, 0.5 mass% with respect to the total amount of the polymerizable liquid crystal composition of the present invention.
When the content of the compound represented by the general formula (P) is small, the effect of the polymerizable compound is hardly exhibited, and the liquid crystal composition has a problem that the orientation-restraining force is weak or the liquid crystal composition becomes weak with time. On the other hand, if the content of the compound represented by the general formula (P) is too large, there are problems that the amount of the unreacted polymerizable compound remaining after curing becomes large, the curing takes time, the reliability of the liquid crystal is lowered, and the like.
Examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulae (P-1-1) to (P-1-46).
[ solution 78]
[ solution 79]
[ solution 80]
[ solution 81]
[ solution 82]
(in the formula, Pp11、Pp12、Spp11And Spp12Represents P in the general formula (P)p1、Pp2、Spp1And Spp2The same meaning is used. )
Preferable examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulae (P-2-1) to (P-2-14).
[ solution 83]
[ solution 84]
(in the formula, Pp21、Pp22、Spp21And Spp22Represents P in the general formula (P)p1、Pp2、Spp1And Spp2The same meaning is used. )
Preferable examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulae (P-3-1) to (P-3-15).
[ solution 85]
[ solution 86]
(in the formula, Pp31、Pp32、Spp31And Spp32Represents P in the general formula (P)p1、Pp2、Spp1And Spp2The same meaning is used. )
Preferable examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulae (P-4-1) to (P-4-21).
[ solution 87]
[ solution 88]
[ solution 89]
[ solution 90]
(in the formula, Pp41、Pp42、Spp41And Spp42Represents P in the general formula (P)p1、Pp2、Spp1And Spp2The same meaning is used. )
(others)
The polymerizable liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, a conventional nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an infrared absorber, and the like. The polymerizable liquid crystal composition of the present invention may or may not contain a self-aligning compound. The spontaneous alignment compound is a compound that can achieve vertical alignment of liquid crystal molecules even without an alignment film, and is represented by, for example, the following formula (Q).
[ solution 91]
MES-R2 (Q)
(in the formula (Q), MES is mesogenic group, which contains each directly or indirectly connected more than 1 ring and directly or via a spacer connected to MES as arbitrary components of more than 1 polymerizable group,
R2are polar anchoring groups preferably comprising at least 1-OH or primary or secondary amine function. )
The polymerizable liquid crystal composition of the present invention preferably has a negative dielectric anisotropy (Δ ∈) and an absolute value of more than 2. The preferable range of the dielectric anisotropy of the polymerizable liquid crystal composition of the present invention may be the same as the range of the dielectric anisotropy of the liquid crystal composition of the present invention described above. The polymerizable liquid crystal composition of the present invention has refractive index anisotropy (Δ n), viscosity (η), and rotational viscosity (γ)1) And nematic phase-isotropic liquid phase transition temperature (T)ni) The preferable ranges of (d) may be set to the refractive index anisotropy (Δ n), viscosity (η), and rotational viscosity (γ) of the liquid crystal composition of the present invention1) And nematic phase-isotropic liquid phase inversionTemperature (T) of changeni) The same applies to the range of (1).
The polymerizable liquid crystal composition of the present invention can be used for liquid crystal display devices, and can be suitably used for liquid crystal display devices for active matrix driving in particular. The polymerizable liquid crystal composition of the present invention can be suitably used for liquid crystal display elements of PSA type, PSVA type, VA type, IPS type, FFS type, or ECB type. Further, the polymerizable liquid crystal composition of the present invention can be suitably used for a liquid crystal display element having a pair of alignment films facing each other with a liquid crystal layer interposed therebetween. When the polymerizable liquid crystal composition of the present invention contains a self-aligning compound, it can also be used for a liquid crystal display element not having an alignment film.
Liquid crystal display element
The liquid crystal display device of the present invention is a device using the polymerizable liquid crystal composition described in the above "i. The liquid crystal display device of the present invention can exhibit a high VHR by using the polymerizable liquid crystal composition, and has excellent display quality without causing or suppressing display defects.
The liquid crystal display element of the present invention is preferably a liquid crystal display element for active matrix driving. The liquid crystal display element of the present invention may be a PSA type, PSVA type, VA type, IPS type, FFS type, or ECB type liquid crystal display element, and is preferably a PSA type or PSVA type liquid crystal display element.
Fig. 1 is a schematic diagram showing an example of a liquid crystal display element of the present invention. The structure of the liquid crystal display element of the present invention is not limited to this example. In fig. 1, the respective components are shown separately for convenience of explanation. The liquid crystal display element 1 shown in fig. 1 includes a first substrate 2 and a second substrate 3 disposed to face each other, and a liquid crystal layer 4 provided between the first substrate 2 and the second substrate 3. The liquid crystal layer 4 includes the liquid crystal composition described in the above "i. Although not shown in the figure, the polymer of the polymerizable compound is localized on the substrates 2 and 3 side in the liquid crystal layer 4. That is, it is considered that a layer made of a polymer of a polymerizable compound is formed at the interface of the liquid crystal layer.
As illustrated in fig. 1, the first substrate 2 has a pixel electrode layer 5 formed on a surface thereof on the liquid crystal layer 4 side. In the second substrate 3, a common electrode layer 6 is formed on the liquid crystal layer 4 side. The first substrate 2 and the second substrate 3 may be sandwiched by a pair of polarizing plates 7, 8. On the liquid crystal layer 4 side of the second substrate 3, a color filter 9 may be further provided.
Further, although not shown in the drawings, in the liquid crystal display device of the present invention, alignment films such as polyimide alignment films are provided on the liquid crystal layer sides of the first substrate and the second substrate, respectively, and the pair of alignment films face each other with the liquid crystal layer interposed therebetween.
That is, as one aspect, the liquid crystal display element of the present invention may have a configuration in which a first polarizing plate, a first substrate, a first alignment film, a pixel electrode layer, a liquid crystal layer including a polymer of a liquid crystal composition and a polymerizable compound, a common electrode layer, a color filter, a second alignment film, a second substrate, and a second polarizing plate are sequentially stacked. In other words, the liquid crystal display device of the present invention has the following configuration: the liquid crystal layer comprises a liquid crystal composition containing at least a polymer of the polymerizable compound in the polymerizable liquid crystal composition described in the above item "i.
The liquid crystal display element of the present invention can be manufactured by a known method. For example, the liquid crystal display element of the present invention can be manufactured as follows: the polymerizable liquid crystal composition was injected between 2 substrates by a vacuum injection method or a Drop Fill (ODF) method, and the polymerizable compound was polymerized by irradiation with active energy rays such as ultraviolet rays or electron beams while the liquid crystal molecules were aligned by applying a voltage, thereby fixing the alignment of the liquid crystal molecules.
The present invention is not limited to the above embodiments. The above-described embodiments are merely illustrative, and it is needless to say that embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and achieving the same operational effects are also included in the technical scope of the present invention.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples.
The compounds described in the examples are abbreviated as follows.
(side chain)
-n -CnH2n+1Straight-chain alkyl group having n carbon atoms
n- CnH2n+1-a linear alkyl group having n carbon atoms
-On -OCnH2n+1Straight-chain alkoxy group having n carbon atoms
nO- CnH2n+1O-straight-chain alkoxy group having n carbon atoms
-V -CH＝CH2
V- CH2＝CH-
-V1 -CH＝CH-CH3
1V- CH3-CH＝CH-
-2V -CH2-CH2-CH＝CH2
V2- CH2＝CH-CH2-CH2-
-2V1 -CH2-CH2-CH＝CH-CH3
1V2- CH3-CH＝CH-CH2-CH2-
(linker)
-CFFO- -CF2-O-
-OCFF- -O-CF2-
-1O- -CH2-O-
-O1- -O-CH2-
-COO- -COO-
-OCO- -OCO-
(Ring structure)
< Compound (H) (light stabilizer) >
As the light stabilizer (polymerizable light stabilizer) represented by the general formula (H), the following compounds were used.
[ solution 92]
< ultraviolet absorber >
As the ultraviolet absorber, the following compounds were used.
[ solution 93]
[ solution 94]
< antioxidant >
As the antioxidant, the following compounds were used.
[ solution 95]
< polymerization initiator >
As the polymerization initiator, the following compounds were used.
[ solution 96]
< non-polymerizable light stabilizer >
The following compounds were used as the non-polymerizable light stabilizer.
[ solution 97]
< polymerizable Compound >
As the polymerizable compound, the following compounds were used.
[ solution 98]
The liquid crystal composition examples used in examples and comparative examples were measured, and the obtained characteristics were as follows.
Tni: nematic phase-isotropic liquid phase transition temperature (. degree.C.)
Δ n: refractive index anisotropy at 25 DEG C
Δ ε: anisotropy of dielectric constant at 25 DEG C
γ1: rotational tack at 25 ℃ (mPa. multidot.s)
The evaluation methods of the Voltage Holding Ratio (VHR) of the liquid crystal cells obtained in the examples and comparative examples are as follows.
VHR (A): the obtained liquid crystal cell was irradiated with ultraviolet light using a fluorescent lamp at an intensity of 313nm of 0.3mW, and then irradiated with VHR for 90 minutes. The VHR was measured at 1V, 0.6Hz and 60 ℃.
VHR (B): the obtained liquid crystal cell was irradiated with ultraviolet light using a fluorescent lamp at an intensity of 313nm of 0.3mW for 90 minutes, and then allowed to stand in a dark room at 60 ℃ for 240 hours, followed by obtaining VHR. The VHR measurement conditions were the same as for VHR (A).
Δ VHR: VHR reduction value [ VHR (A) -VHR (B) ]caused by storage of unit under high-temperature condition
(preparation of mother composition)
The following base compositions LC-A to LC-C were prepared, and their physical property values were measured. The composition of each base composition and the results of the physical property values are shown in tables 1 to 3.
[ Table 1]
| LC-A | (wt％) |
| 3-Ph-Ph-1 | 8 |
| 3-Cy-Cy-V | 29 |
| 3-Cy-Cy-2 | 5 |
| 3-Cy-1O-Ph5- |
8 |
| 3-Cy-1O-Ph5- |
8 |
| 3-Cy-Cy-1O-Ph5-O2 | 14 |
| 3-Cy-Cy-1O-Ph5-O4 | 12 |
| 3-Cy-Ph-Ph5- |
8 |
| 3-Cy-Ph-Ph5- |
8 |
| Total up to | 100 |
| Tni(℃) | 76 |
| Δn | 0.109 |
| γ1 | 95 |
| Δε | -3.6 |
[ Table 2]
| LC-B | (wt％) |
| 3-Ph-Ph-1 | 8 |
| 3-Cy-Cy-V | 29 |
| 3-Cy-Cy-2 | 5 |
| 3-Ph-Ph5-02 | 4 |
| 3-Cy-Ph5-02 | 4 |
| 3-Cy-1O-Ph5-O1 | 4 |
| 3-Cy-1O-Ph5-O2 | 4 |
| 3-Cy-Cy-1O-Ph5-O2 | 14 |
| 3-Cy-Cy-1O-Ph5-O4 | 12 |
| 3-Cy-Ph-Ph5- |
8 |
| 3-Cy-Ph-Ph5- |
8 |
| Total up to | 100 |
| Tni(℃) | 76 |
| Δn | 0.111 |
| γ1 | 93 |
| Δε | -3.7 |
[ Table 3]
| LC-C | (wt％) |
| 3-Ph-Ph-1 | 8 |
| 3-Cy-Cy-V | 29 |
| 3-Cy-Cy-2 | 5 |
| 3-Cy-CFFO-Ph5-O2 | 4 |
| 3-Cy-1O-Ph5-O1 | 4 |
| 3-Cy-1O-Ph5- |
8 |
| 3-Cy-Cy-1O-Ph5-O2 | 14 |
| 3-Cy-Cy-1O-Ph5-O4 | 12 |
| 3-Cy-Ph-Ph5- |
8 |
| 3-Cy-Ph-Ph5- |
8 |
| Total up to | 100 |
| Tni(℃) | 76.4 |
| Δn | 0.109 |
| γ1 | 97 |
| Δε | -3.7 |
(example 1)
A polymerizable liquid crystal composition LC-1 (see Table 4) was prepared by adding 0.05 part by mass of the compound of formula (H-1) as a polymerizable light stabilizer and 0.3 part by mass of the compound of formula (M-1) as a polymerizable compound to 100 parts by mass of the matrix composition LC-A. T of polymerizable liquid Crystal composition LC-1niΔ n, Δ ε and γ1Same as the parent composition LC-a. Next, after injecting the polymerizable liquid crystal composition LC-1 into a cell having a gap of 3.5um of a vertical alignment film (JALS2096) on a transparent electrode in vacuum, an adhesive (3026B) was applied to the injection port, and then, ultraviolet rays of 380nm were irradiated for 10 seconds to seal the cell, thereby obtaining a liquid crystal cell. The resultant liquid crystal cell had VHR (1), VHR (b) 76%, and Δ VHR 7% (see table 5).
(examples 2 to 6)
The respective compounds were added to 100 parts by mass of the mother composition LC-A in the ratios shown in Table 4 to prepare polymerizable liquid crystal compositions LC-2 to LC-12. In table 4, the parenthesized values indicate the amounts (parts by mass) of the compounds to be added. T of polymerizable liquid Crystal compositions LC-2 to LC-12niΔ n, Δ ε and γ1Same as the parent composition LC-a.
The same applies to tables 6 and 8 below. Next, liquid crystal cells were produced using the polymerizable liquid crystal compositions LC-2 to LC-12, respectively, in the same manner as in example 1, and VHR (a), VHR (b), and Δ VHR of each liquid crystal cell were measured. The results are shown in Table 5.
Comparative examples 1 to 6
Relative to 100 parts by mass of the parent composition LC-AThe respective compounds were added in the proportions shown in Table 4 to prepare polymerizable liquid crystal compositions LC-7 to LC-12, respectively. T of each of polymerizable liquid crystal compositions LC-7 to LC-12niΔ n, Δ ε and γ1Same as the parent composition LC-a. Next, liquid crystal cells were produced in the same manner as in example 1 using the polymerizable liquid crystal compositions LC-7 to LC-12, and the liquid crystal cells VHR (a), VHR (b), and Δ VHR were measured. The results are shown in Table 5.
[ Table 4]
[ Table 5]
A comparison of example 1 with comparative example 1 shows that by adding a compound of formula (H) to a parent composition comprising a compound represented by general formula (II), the values of VHR (1) and VHR (2) become higher and the value of Δ VHR becomes smaller. Further, as shown by comparison of example 1 with comparative examples 2 to 3, the liquid crystal cell using the polymerizable liquid crystal composition containing the polymerizable light stabilizer represented by formula (H) exhibited high VHR (1) and VHR (2) and the value of Δ VHR was smaller than the liquid crystal cell using the polymerizable liquid crystal composition containing a non-polymerizable light stabilizer. In particular, a comparison between example 1 and comparative example 2 shows that if the amount of the addition is the same, when a polymerizable light stabilizer is used, the reduction in VHR due to high VHR and high temperature holding is suppressed. Further, a comparison between example 1 and comparative examples 4 to 6 shows that the polymerizable liquid crystal composition containing the compound represented by the general formula (H) has higher VHR (1) and VHR (2) values and smaller Δ VHR values than the polymerizable liquid crystal composition containing the compound represented by the general formula (II) and containing other additives such as an ultraviolet absorber, an antioxidant, and a polymerization initiator.
(examples 7 to 21)
The respective compounds were added to 100 parts by mass of the mother composition LC-A in the ratios shown in Table 6 to prepare polymerizable liquid crystal compositions LC-13 to LC-27. T of each of polymerizable liquid crystal compositions LC-13 to LC-27niΔ n, Δ ε and γ1Same as the parent composition LC-a. Next, liquid crystal cells were produced in the same manner as in example 1 using the polymerizable liquid crystal compositions LC-13 to LC-27, respectively. VHR (A), VHR (B), and Δ VHR of each liquid crystal cell were measured. The results are shown in Table 7.
[ Table 6]
[ Table 7]
Shows that: the VHRs (A), VHRs (B), and Δ VHRs of examples 7-21 were improved as compared to comparative examples 4-6. That is, in examples 7 to 21 in which the compound represented by the general formula (H) and the other additives were added in combination to the polymerizable liquid crystal composition containing the compound represented by the general formula (II), the improvement effects of VHR (1), VHR (2), and Δ VHR were higher than those of comparative examples 4 to 6 in which the other additives were added alone. From these results, it can be presumed that: VHR is complementarily improved by the action function of the compound represented by the general formula (H), the function of inhibiting the decomposition of the liquid crystal composition by ultraviolet irradiation with an ultraviolet absorber, the function of repairing the decomposition product of the liquid crystal composition by ultraviolet irradiation during high-temperature storage with an antioxidant, and the function of improving the insulation of the liquid crystal cell by a polymerization initiator.
(examples 22 to 29)
The respective compounds were added to 100 parts by mass of the mother compositions LC-B and LC-C in the ratios shown in Table 8 to prepare polymerizable liquid crystal compositions LC-28 to LC-35. T of each of polymerizable liquid crystal compositions LC-28 to LC-31ni、Δn、ΔεAnd gamma1Same as the parent composition LC-B. T in each of the polymerizable liquid crystal compositions LC-32 to LC-35niΔ n, Δ ε and γ1Same as the parent composition LC-C. Then, liquid crystal cells were produced in the same manner as in example 1 using each of the polymerizable liquid crystal compositions LC-28 to LC-35. VHR (A), VHR (B), and Δ VHR of each liquid crystal cell were measured. The results are shown in Table 9.
[ Table 8]
[ Table 9]
From the results of examples 22 to 29, it was confirmed that the addition of the compound represented by the general formula (H) can improve the reliability even when the composition of the polymerizable liquid crystal composition containing the compound represented by the general formula (II) is changed. Further, even when the composition of the polymerizable liquid crystal composition is changed, it is shown that a complementary reliability-improving effect is obtained when an ultraviolet absorber, an antioxidant and a polymerization initiator are used in combination in addition to the compound represented by the general formula (H).
As described above, it was confirmed that the light stabilizer represented by the general formula (H) has a higher effect of suppressing deterioration of the polymerizable liquid crystal composition containing the compound represented by the general formula (II) than the non-polymerizable light stabilizer and other additives. Further, it is shown that the polymerizable liquid crystal composition of the present invention contains at least the light stabilizer represented by the general formula (H), the compound represented by the general formula (II), and the polymerizable compound, and thus has high Δ ∈ and reliability, and high stability against external stimulus. Further, the liquid crystal display devices using the polymerizable liquid crystal compositions obtained in examples 1 to 29 showed no display defects and exhibited sufficient response speed for television applications.
Claims (11)
1. A polymerizable liquid crystal composition having a negative dielectric anisotropy, comprising 1 or more polymerizable compounds having 1 or more polymerizable groups in 1 molecule, 1 or more light stabilizers represented by the general formula (H), and 1 or more liquid crystal compounds represented by the general formula (II),
[ solution 1]
In the general formula (H), T is a group represented by the following formula (1),
[ solution 2]
In the formula (1), Ra, Rb, Rc and Rd independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, Ra and Rb and/or Rc and Rd may be bonded to each other to form a ring,
rg represents a hydrogen atom, a hydroxyl group, -O-, or an alkyl group having 1 to 12 carbon atoms, and 1 or 2 or more-CH groups not adjacent to each other are present in the alkyl group2-independently from each other may be-O-, -S-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH-COO-, -CH-OCO-, -COO-CH-, -OCO-CH-, -CH-, -C.ident.C-, -Si (CH ≡ C)3)2-, trans-1, 4-cyclohexylene, 1, 4-phenylene or naphthalene-2, 6-diyl, 1 or 2 or more hydrogen atoms in Rg may be independently substituted with a halogen atom or a cyano group,
nT1and nT2Each independently represents 0, 1,2 or 3, nT1+nT2Represents 1,2,3 or 4,
the black dots represent the connecting keys and,
AH1and AH2Independently represent a 2-valent aromatic group, a 2-valent cycloaliphatic group, a 2-valent heterocyclic compound group, a 2-valent condensed ring and a 2-valent condensed polycyclic group, wherein more than 1 hydrogen atom in the ring structure can be replaced by a group LH1Or RH1-(AH3-ZH3)m H2-is substituted, AH1And AH2One of them may represent a single bond,
AH3represents a 2-valent aromatic group, a 2-valent cycloaliphatic group, a 2-valent heterocyclic compound group, a 2-valent condensed ring and a 2-valent condensed polycyclic ring, wherein more than 1 hydrogen atom in the ring structure can be replaced by a group LH1The substitution is carried out by the following steps,
ZH1、ZH2and ZH3Independently represent-O-, -S-, -CO-O-, -O-CO-O-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n-、-CF2CH2-、-CH2CF2-、-(CF2)n-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH2-CH2-CO-O-、-O-CO-CH2-CH2-、-CRH2RH3-or single bonds, in which more than one hydrogen atom may be replaced by a group LH1Or RH1-(AH3-ZH3)m H2-a substitution of a group of formula (I),
LH1represents PH2-SpH2-, a group T, a fluorine atom, a chlorine atom, a cyano group, or a C1-25 linear, branched or cyclic alkyl group, wherein at least 1 of the alkyl groups is not adjacent to a-CH2May be substituted by-O-, -S-, -CO-O-, -O-CO-O-in such a way that oxygen atoms and/or sulfur atoms are not linked directly to one another, and 1 or more hydrogen atoms in the alkyl group may be replaced by fluorine atoms, chlorine atoms or PH2-SpH2-a substitution of a group of formula (I),
PH1and PH2Each independently represents a hydrogen atom or a polymerizable group,
SpH1and SpH2Each independently represents a spacer or a single bond,
RH1represents PH2-SpH2A hydrogen atom, a fluorine atom, a chlorine atom, or a carbon atom number of 1 to 25A straight, branched or cyclic alkyl group of which at least 1 or more of-CH's are not adjacent2May be substituted by-O-, -S-, -CO-O-, -O-CO-O-in such a way that oxygen atoms and/or sulfur atoms are not linked directly to one another, and 1 or more hydrogen atoms in the alkyl group may be replaced by fluorine atoms, chlorine atoms or P atomsH2-SpH2-a substitution of a group of formula (I),
RH2and RH3Each independently represents a hydrogen atom or an alkylene group having 1 to 12 carbon atoms,
mH1represents 0, 1,2,3 or 4,
mH2represents 0, 1,2,3 or 4,
n represents 1,2,3 or 4,
PH2、SpH2、LH1、AH1、AH2、AH3、ZH2、ZH3、RH1and T, the symbols may be the same or different,
wherein the general formula (H) has 1 or more polymerizable groups in the molecule,
[ solution 3]
In the formula, RII1And RII2Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 or 2 or more-CH groups not adjacent to each other in the alkyl group2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,
AII1、AII2and AII3Each independently represents a group selected from the group consisting of,
(a)1, 4-cyclohexylene radical, 1-CH present in this radical2-or 2 or more-CH not adjacent2-may be substituted by-O-;
(b)1, 4-phenylene, 1-CH ═ or nonadjacent 2 or more-CH ═ present in the group can be substituted by-N ═ or;
(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl, wherein 1-CH ═ or 2 or more noncontiguous-CH ═ groups present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-N ═ groups; and
(d)1, 4-Cyclohexenylene group
The group (a), the group (b), the group (c) and the group (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,
ZII1and ZII2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,
nII1and nII2Each independently represents an integer of 0 to 2, nII1+nII2Is a number of 0, 1 or 2,
AII1and AII2When a plurality of the compounds are present, they may be the same or different,
ZII1and ZII2When a plurality of the compounds are present, they may be the same or different.
2. The polymerizable liquid crystal composition according to claim 1, further comprising 1 or more compounds represented by the following general formula (L-1A),
[ solution 4]
In the general formula (L-1A), RL11AAnd RL12AEach independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent 2 or more-CH2-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-, RL11AAnd RL12A1 or non-adjacent 2 or more-CH in the alkyl group2-is independently substituted with-CH ═ CH-.
3. The polymerizable liquid crystal composition according to claim 1 or 2, comprising 1 or more compounds represented by the following general formula (P) as the polymerizable compound,
[ solution 5]
In the above general formula (P), Rp1Represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or-Spp2-Pp21 or non-adjacent 2 or more-CH groups in the alkyl group2-each independently may be substituted by-CH- ═ CH-, -C.ident.C-, -O-, -CO-, -COO-or-OCO-, and 1 or more than 2 hydrogen atoms in the alkyl group may each independently be substituted by cyano groups, fluorine atoms or chlorine atoms,
Pp1and Pp2Each independently represents a general formula (P)p1-1) to formula (P)p1-any one of the above-mentioned-9),
[ solution 6]
In the formula, Rp11And Rp12Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms, Wp11Represents a single bond, -O-, -COO-or methylene, tp11Represents 0, 1 or 2, and a plurality of R exist in the moleculep11、Rp12、Wp11And/or tp11They may be the same or different,
Spp1and Spp2Each independently represents a single bond or a spacer,
Zp1and Zp2Each independently represents a single bond, -O-, -S-, -CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRZP1-、-NRZP1-CO-、-SCH2-、-CH2S-、-CH＝CRZP1-COO-、-CH＝CRZP1-OCO-、-COO-CRZP1＝CH-、-OCO-CRZP1＝CH-、-COO-CRZP1＝CH-COO-、-COO-CRZP1＝CH-OCO-、-OCO-CRZP1＝CH-COO-、-OCO-CRZP1＝CH-OCO-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-(C＝O)-O-(CH2)2-、-CH＝CH-、-CF＝CF-、-CF＝CH-、-CH＝CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-or-C ≡ C-, wherein R isZP1Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R's are present in the moleculeZP1They may be the same or different,
Ap1、Ap2and Ap3Each independently represents a group selected from the group consisting of,
(ap)1, 4-cyclohexylene radical, 1-CH present in this radical2-or 2 or more-CH not adjacent2-may be substituted by-O-;
(bp)1, 4-phenylene, 1-CH ═ or nonadjacent 2 or more-CH ═ present in the group can be substituted by-N ═ or; and
(cp) Naphthalene-2, 6-diyl group, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl group, decahydronaphthalene-2, 6-diyl group, phenanthrene-2, 7-diyl group, or anthracene-2, 6-diyl group, wherein 1-CH ═ or 2 or more-CH ═ groups which are not adjacent to each other and are present in these groups may be substituted with-N ═ and hydrogen atoms present in the groups may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 1 to 8 carbon atoms,
the above group (a)p) Group (b)p) And a group (c)p) Wherein 1 or 2 or more hydrogen atoms present in the group (a) are independently a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms or-Spp2-Pp2Substituted, 1 or non-adjacent 2 or more-CH in the alkyl group2-each independently may be-CH ═ CH-, -C ≡ andc-, -O-, -CO-, -COO-or-OCO-substituted,
mp1represents 0, 1,2 or 3, and a plurality of Z's are present in the moleculep1、Ap2、Spp2And/or Pp2When they are the same or different, in mp1Is 0 and Ap1When it is phenanthrene-2, 7-diyl or anthracene-2, 6-diyl, Ap3Represents a single bond, and is a hydrogen atom,
wherein the compound represented by the general formula (H) is excluded.
4. The polymerizable liquid crystal composition according to any one of claims 1 to 3, comprising 1 or more compounds selected from the group consisting of an antioxidant, an ultraviolet absorber, and a polymerization initiator.
5. The polymerizable liquid crystal composition according to claim 4, comprising 1 or more hindered phenol antioxidants.
6. The polymerizable liquid crystal composition according to claim 4 or 5, comprising at least one of 1 or more of a benzophenone-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber.
7. The polymerizable liquid crystal composition according to any one of claims 4 to 6, comprising 1 or more benzil ketal polymerization initiators.
8. The polymerizable liquid crystal composition according to any one of claims 4 to 7, wherein the total amount of the compound represented by the general formula (H) and 1 or more compounds selected from the group consisting of the ultraviolet absorber, the antioxidant and the polymerization initiator is in the range of 0.005 to 0.2% by mass.
9. The polymerizable liquid crystal composition according to any one of claims 1 to 8, which is used for producing a liquid crystal display element provided with a pair of alignment films facing each other with a liquid crystal layer interposed therebetween.
10. A liquid crystal display element using the polymerizable liquid crystal composition according to any one of claims 1 to 9.
11. A liquid crystal display element has a pair of alignment films facing each other with a liquid crystal layer interposed therebetween,
the liquid crystal layer includes a liquid crystal composition containing at least a polymer of the polymerizable compound in the polymerizable liquid crystal composition according to any one of claims 1 to 9, the light stabilizer represented by the general formula (H), and the liquid crystal compound represented by the general formula (II).
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