Patent Grant
10000700
The present invention relates to a nematic liquid crystal composition that is useful as an electro-optical liquid crystal display material and has positive dielectric anisotropy (Δ∈).
Liquid crystal display devices are increasingly used in watches, calculators, various measurement instruments, automobile panels, word processors, electronic organizers, printers, computers, televisions, clocks, advertising boards, etc. Representative examples of the liquid crystal display mode include twisted nematic (TN) mode, super twisted nematic (STN) mode, VA mode that is characterized by vertical alignment and use of thin film transistors (TFTs), and in-plane-switching (IPS)/FFS mode characterized by horizontal alignment. Liquid crystal compositions used in these liquid crystal display devices are required to be stable against external factors such as moisture, air, heat, and light, exhibit a liquid crystal phase in a temperature range as wide as possible with room temperature at the center, have low viscosity, and operate at low drive voltage. A liquid crystal composition is composed of several to dozens of compounds in order to optimize dielectric anisotropy (Δ∈) and/or refractive index anisotropy (Δn) and the like for each individual display device.
A vertical alignment display uses a liquid crystal composition with a negative Δ∈ and a horizontal alignment display such as a TN, STN, or IPS display uses a liquid crystal composition having a positive Δ∈. Recently, there has been a report of a drive mode with which a liquid crystal composition having a positive Δ∈ is aligned vertically in the absence of the applied voltage and a horizontal electric field is applied as in the IPS/FFS mode devices. There is now increasing need for liquid crystal compositions with positive Δ∈. Meanwhile, pursuit for lower voltage drive, high speed response, and wide operation temperature range is common for all driving modes. In other words, a positive Δ∈ with a large absolute value, low viscosity (η), and a high nematic phase-isotropic liquid phase transition temperature (Tni) are being required. Due to the setting of the product of Δn and the cell gap (d), i.e., Δn×d, the Δn of the liquid crystal composition must be adjusted to be in an appropriate range for the cell gap. Moreover, when the liquid crystal display device is to be adopted to televisions etc., high response speed is important and thus a liquid crystal composition with small γ1 is required.
Liquid crystal compositions that use a compound having a positive Δ∈ represented by formula (A-1) or (A-2) as a constitutional component of the liquid crystal composition have been disclosed (PTL 1 and PTL 2). However, these liquid crystal compositions did not achieve sufficiently low viscosity. There have also been disclosure of compounds having a —CF2O— linking group represented by formulae (A-3) and (A-4) and liquid crystal compositions that use these compounds. However, these liquid crystal compositions also did not achieve sufficiently low viscosity (PTL 3 and PTL 4).
An object of the present invention is to provide a highly reliable, positive dielectric anisotropy (Δ∈) liquid crystal composition having the dielectric anisotropy (Δ∈) and refractive index anisotropy (Δn) adjusted to desired levels, in which a decrease in nematic phase-isotropic liquid phase transition temperature (Tni) and an increase in the nematic phase lower limit temperature are suppressed so as not to degrade the nematic phase temperature range, the viscosity (η) is sufficiently low, and the response speed is high when the composition is used in a liquid crystal display device.
The inventors of the present invention have studied various fluorobenzene derivatives and found that the object described above can be achieved by a combination of particular compounds. Thus, the present invention has been made.
The present invention provides a liquid crystal composition having positive dielectric anisotropy. The liquid crystal composition contains at least one compound represented by general formula (LC0):
(In the formula, R01 represents an alkyl group having 1 to 15 carbon atoms, one or more CH2 groups in the alkyl group may each be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF2O—, or —OCF2— so long as oxygen atoms are not directly adjacent to each other, one or more hydrogen atoms in the alkyl group may each be substituted with a halogen, A01 and A02 each independently represent a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 1,4-cyclohexenylene group, a 1,4-bicyclo[2.2.2]octylene group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, B01 represents one of the following structures:
(In the structures, X01, X02, X05, X06, and X07 each independently represent a hydrogen atom or a fluorine atom and Y01 and Y02 each independently represent a chlorine atom, a cyano group, a fluorine atom, —CF3, or —OCF3), Z01, Z02, and Z03 each independently represent a single bond, —CH═CH—, —C≡C—, —CH2CH2—, —(CH2)4—, —OCH2—, —CH2O—, —OCF2—, or —CF2O—, X03 and X04 each independently represent a hydrogen atom or a fluorine atom, m01 and m02 each independently represent an integer of 0 to 2, m01+m02 is 0, 1, or 2, and when two or more A01, A02, Z01, and/or Z03 are present, they may be the same or different), and at least one compound represented by general formula (LC1):
[Chem. 4]
R11A11-Z11
m
(In the formula, R11 and R12 each independently represent an alkyl group having 1 to 15 carbon atoms, one or more —CH2— in the alkyl group may each be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF2O—, or —OCF2— so long as oxygen atoms are not directly adjacent to each other, one or more hydrogen atoms in the alkyl group may each be substituted with a halogen, A11 to A13 each independently represent a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 1,4-cyclohexenylene group, a tetrahydropyran-2,5-diyl group, a 1,3-dioxane-2,5-diyl group, a 1,4-bicyclo[2.2.2]octylene group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, Z11 and Z12 each independently represent a single bond, —CH═CH—, —C≡C—, —CH2CH2—, —(CH2)4—, —OCH2—, —CH2O—, —OCF2—, or —CF2O—, m11 represents 0, 1, or 2, and when two or more A11 and/or Z11 are present, they may be the same or different). Also provided is a liquid crystal display device that uses this liquid crystal composition.
A liquid crystal composition according to the present invention has a positive Δ∈ having an absolute value adjusted to the desired level and refractive index anisotropy (Δn) adjusted to the desired level, has low rotational viscosity (γ1) and excellent liquid crystal properties, and exhibits a stable liquid crystal phase in a wide temperature range. Moreover, since the liquid crystal composition is chemically stable against heat, light, water, etc., and has good solubility, low-temperature phase stability is excellent. When the liquid crystal composition according to the present invention is used to form a liquid crystal display device, a highly useful, high-reliability liquid crystal display device having high response speed and enabling low-voltage driving is obtained.
The liquid crystal composition according to the invention of the present application contains at least one compound represented by general formula (LC0) and at least one compound represented by general formula (LC1). Because a liquid crystal composition that contains a compound represented by general formula (LC0) and a compound represented by general formula (LC1) has a positive Δ∈ and has the absolute value of Δ∈ and the refractive index anisotropy (Δn) adjusted to desired levels, has low viscosity, and exhibits a stable liquid crystal phase at low temperatures, the liquid crystal composition can be regarded as a highly useful liquid crystal composition.
In general formula (LC0):
R01 preferably represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms and more preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms in order to decrease viscosity. R01 is preferably linear. When R01 represents an alkenyl group, it is preferably selected from the groups represented by formula (R1) to formula (R5) (in each formula, the black dot represents a linking point to a ring). When A01 represents a trans-1,4-cyclohexylene group, these alkenyl groups are preferable and formula (R1), formula (R2), and formula (R4) are more preferable.
A01 and A02 preferably each independently represent a trans-1,4-cyclohexylene group, a naphthalene-2,6-diyl group, or a 1,4-phenylene group and more preferably a trans-1,4-cyclohexylene group in order to decrease viscosity. In order to increase Δ∈, A01 and A02 preferably each independently represent a 3-fluoro-1,4-phenylene group or a 3,5-difluoro-1,4-phenylene group and more preferably a 3,5-difluoro-1,4-phenylene group. In order to increase T→i, a trans-1,4-cyclohexylene group or a 1,4-phenylene group is preferable.
In order to decrease viscosity, B01 preferably represents the following:
In order to increase T→i,
the above is preferable.
X01, X02, X05, X06, and X07 preferably each independently represent a hydrogen atom in order to decrease viscosity and increase T→i. In order to increase Δ∈, a fluorine atom is preferable.
When X01 and X02 each independently represent a fluorine atom or a hydrogen atom, the following is preferable in order to increase Δ∈:
In order to decrease viscosity,
the above is preferable.
When X05 to X07 each independently represent a fluorine atom or a hydrogen atom, the following is preferable in order to increase Δ∈:
In order to decrease viscosity,
the above is preferable.
B01 is particularly preferably any one selected from the following partial structures:
Y01 and Y02 preferably each represent a fluorine atom, —CF3, or —OCF3 in order to improve the nematic phase lower limit temperature and enhance low-temperature operation and storage property of the liquid crystal composition. In order to increase ΔΣ, a fluorine atom, a cyano group, —CF3, or —OCF3 is preferable, and in order to decrease viscosity, a fluorine atom is preferable. In view of stability of the compound, a fluorine atom, —CF3, or —OCF3 is preferable.
X03 and X04 each independently represent a hydrogen atom or a fluorine atom; however, in order to increase Δ∈, a fluorine atom is preferable and in order to improve solubility, a fluorine atom is preferable. At least one selected from X03 and X04 preferably represents a fluorine atom and more preferably X03 and X04 both represent a fluorine atom from the viewpoint of ΔΣ and solubility.
In order to decrease viscosity, Z1, Z2, and Z3 preferably each independently represent —CH2O—, —OCH2—, —CF2O—, —OCF2—, —CF═CF—, —CH2CH2—, —CH═CH—, —C≡C—, or a single bond, more preferably —CF2O—, —OCF2—, —CH2CH2—, or a single bond, and yet more preferably a single bond. In order to increase T→i, —C≡C— or a single bond is preferable.
When q is of importance, m01 and m02 preferably satisfy m01+m02=0 or 1. When m01+m02=1, m01 preferably represents 0 and m02 preferably represents 1. When T→i is of importance, m01+m02 is preferably 1 or 2. In order to increase miscibility with the liquid crystal composition, m01+m02 is preferably 0 or 1.
In a compound represented by general formula (0), hetero atoms are never directly bonded to each other.
In a compound represented by general formula (0), the number of F substitution in general formula (LC0) is preferably 2 to 7.
The compound represented by general formula (LC0) is preferably a compound that satisfies at least one of the following items:
The liquid crystal compound represented by general formula (LC0) is more preferably a compound represented by any of general formulae (LC0-a) to (LC0-j) below (in the formula, R01, A01, A02, X01 to X07, Y01, and Y02 are the same as R01, A01, A02, X01 to X06, Y01, and Y02 in general formula (LC0) and X08 to X13 each represent a hydrogen atom or a fluorine atom). The liquid crystal composition of the present invention preferably contains at least one selected from compounds represented by (LC0-a) to (LC0-i) as the compound represented by general formula (LC0).
As the compound represented by general formula (LC0-a), compounds represented by general formula (LC0-a1) to general formula (LC0-a11) below are more preferable and a compound represented by general formula (0-a1) is yet more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-b), compounds represented by general formula (LC0-b1) to general formula (LC0-b24) below are more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-c), compounds represented by general formula (LC0-c1) to general formula (LC0-c17) below are preferable, compounds represented by general formula (LC0-c1) to general formula (LC0-c3) are more preferable, and compounds represented by general formula (LC0-c2) and general formula (LC0-c3) are yet more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-d), compounds represented by general formula (LC0-d1) to general formula (LC0-d9) below are more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-e), compounds represented by general formula (LC0-e1) to general formula (LC0-e8) below are more preferable and compounds represented by general formula (LC0-e1) and general formula (LC0-e8) are yet more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-f), compounds represented by general formula (LC0-f1) to general formula (LC0-f6) below are more preferable and a compound represented by general formula (LC0-f2) is yet more preferable.
(In the formula, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-g), compounds represented by general formula (LC0-g1) to general formula (LC0-g12) below are more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-h), compounds represented by general formula (LC0-h1) to general formula (LC0-h4) below are more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
As the compound represented by general formula (LC0-i), compounds represented by general formula (LC0-i1) to general formula (LC0-i6) below are more preferable.
(In the formulae, R01 is the same as R01 in general formula (LC0).)
When the amount of the compound represented by general formula (LC0) contained in the liquid crystal composition of the present invention is small, the effects thereof do not appear. Thus, the lower limit of the amount in the composition is preferably 0.1% by mass or more (hereinafter, % for the amount in the composition represents % by mass), preferably 0.3% or more, preferably 0.5% or more, preferably 0.8% or more, preferably 1% or more, preferably 2% or more, preferably 3% or more, preferably 4% or more, preferably 5% or more, preferably 6% or more, preferably 7% or more, preferably 8% or more, preferably 9% or more, preferably 10% or more, preferably 13% or more, preferably 15% or more, preferably 18% or more, and preferably 20% or more. Since problems such as precipitation occur at a large amount, the upper limit is 80% or less, preferably 70% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, preferably 48% or less, preferably 45% or less, preferably 43% or less, preferably 40% or less, preferably 38% or less, preferably 37% or less, preferably 35% or less, preferably 32% or less, preferably 30% or less, preferably 28% or less, preferably 25% or less, preferably 23% or less, and preferably 20% or less. The compounds represented by general formula (1) may be used alone or in combination of two or more.
In general formula (LC1):
[Chem. 26]
R11A11-Z11
m
R11 and R12 each independently represent an alkyl group having 1 to 15 carbon atoms, one or more —CH2— in the alkyl group may each be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF2O—, or —OCF2— so long as oxygen atoms are not directly adjacent to each other, and one or more hydrogen atoms in the alkyl group may be substituted with a halogen. However, R11 and R12 preferably each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms and are preferably linear. When R11 and R12 each represent an alkenyl group, the alkenyl group is preferably one selected from formula (R1) to formula (R5).
(In each formula, the black dot represents a linking point to a ring.)
When R11 and R12 each represent an alkenyloxy group, an alkenyl group having 2 to 6 carbon atoms is preferable in order to decrease viscosity and preferably selection is made from the groups represented by formula (R6):
(In the formula, R14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, one —CH2— or two or more non-adjacent —CH2— present in these groups may each be substituted with —O—, —COO—, —OCO—, or —CO—, a hydrogen atom present in these groups may be substituted with a fluorine atom, and the black dot in the formula represents a linking point to a ring.) More preferably, R14 represents a hydrogen atom or a methyl group.
The combination of R11 and R12 is not particularly limited. Both may represent an alkyl group, one may represent an alkyl group while the other may represent an alkenyl group, one may represent an alkyl group while the other may represent an alkoxy group, or one may represent an alkyl group while the other may represent an alkenyloxy group.
A11 to A13 preferably each independently represent one of the following structures:
A11 to A13 each independently represent one of the following structures:
which are more preferable.
Z11 and Z12 each independently represent a single bond, —CH═CH—, —C≡C—, —CH2CH2—, —(CH2)4—, —OCH2—, —CH2O—, —OCF2—, or —CF2O—, more preferably a single bond, —CH2CH2—, —OCF2—, or —CF2O—, and yet more preferably a single bond.
Preferably, m11 represents an integer of 1 or 2. When two or more A11 and/or Z11 are present, they may be the same or different.
The compound represented by general formula (LC1) is preferably selected from the compounds represented by general formula (LC1-1) to general formula (LC1-39) below. The liquid crystal composition according to the present invention preferably contains, as a compound represented by general formula (LC1), at least one selected from the compounds represented by (LC1-1) to (LC1-26), more preferably contains at least one compound represented by (LC1-1) to (LC1-5), (LC1-7), (LC1-15), (LC1-16), (LC1-18), (LC1-21), and (LC1-38):
(In the formulae, R11 and R12 are respectively the same as R11 and R12 in general formula (LC1).)
As the compound represented by general formula (LC1), at least one selected from the group consisting of the following compounds is more preferably contained in an amount of 70% by mass at most.
(In the formulae, alkyl and alkyl* each independently represent an alkyl or alkoxy group having 1 to 5 carbon atoms and alkenyl and alkenyl* each independently represent an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.)
In the liquid crystal composition according to the present invention, the lower limit of the amount of the compound represented by general formula (LC1) is preferably 1% or more, preferably 5% or more, preferably 10% or more, preferably 15% or more, preferably 18% or more, preferably 20% or more, preferably 25% or more, preferably 28% or more, preferably 30% or more, preferably 33% or more, preferably 35% or more, preferably 38% or more, preferably 40% or more, preferably 43% or more, preferably 45% or more, preferably 48% or more, preferably 50% or more, preferably 53% or more, preferably 55% or more, preferably 58% or more, and preferably 60% or more. The upper limit is preferably 99% or less, preferably 98% or less, preferably 95% or less, preferably 93% or less, preferably 90% or less, preferably 87% or less, preferably 85% or less, preferably 83% or less, preferably 80% or less, preferably 88% or less, preferably 85% or less, preferably 83% or less, preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 73% or less, preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 63% or less, and preferably 60% or less. The compounds represented by general formula (1) can be used alone or in combination of two or more.
In the liquid crystal composition according to the present invention, the lower limit of the amount of the compounds represented by general formula (LC0) and general formula (LC1) contained is preferably 5% or more, preferably 10% or more, preferably 15% or more, preferably 20% or more, preferably 25% or more, preferably 30% or more, preferably 35% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more, preferably 65% or more, preferably 70% or more, and preferably 75% or more. The upper limit is preferably 100% or less, preferably 95% or less, preferably 90% or less, preferably 85% or less, preferably 80% or less, preferably 75% or less, preferably 70% or less, preferably 65% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, preferably 40% or less, and preferably 30% or less.
Furthermore, the liquid crystal composition contains a compound represented by general formula (LC2):
[Chem. 35]
R21A21-Z21
m
(In the formula, R21 represents an alkyl group having 1 to 15 carbon atoms, one or more —CH2— in the alkyl group may each be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF2O—, or —OCF2— so long as oxygen atoms are not directly adjacent to each other, one or more hydrogen atoms in the alkyl group may each be substituted with a halogen, A21 and A22 each independently represent a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 1,4-cyclohexenylene group, a tetrahydropyran-2,5-diyl group, a 1,3-dioxane-2,5-diyl group, a 1,4-bicyclo[2.2.2]octylene group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, B21 represents a structure selected from below:
(In the structures, X21 to X25 each independently represent a hydrogen atom or a fluorine atom and Y21 and Y22 each independently represent a chlorine atom, a cyano group, a fluorine atom, —CF3, —OCF3, —CF2CF3, —CHFCF3, —OCF2CF3, —OCHFCF3, or —OCF═CF2), Z21 and Z22 each independently represent a single bond, —CH═CH—, —C≡C—, —CH2CH2—, —(CH2)4—, —OCH2—, —CH2O—, —OCF2—, or —CF2O—, m21 represents 0, 1, 2, or 3, and when two or more A21 and/or Z21 are present, they may be the same or different. However, compounds represented by general formula (LC0) are excluded.)
R21 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 is preferably linear. When R21 represents an alkenyl group, it is preferably selected from groups represented by formula (R1) to formula (R5).
(In each formula, the black dot represents a linking point to a ring.)
A21 and A22 preferably each independently represent a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, or a tetrahydropyran group.
In order to decrease viscosity, B21 preferably represents the following:
In order to increase T→i,
is preferable.
X21, X22, X23, XZ4, and X25 preferably each independently represent a hydrogen atom in order to decrease viscosity and increase T→i, and preferably each independently represent a fluorine atom in order to increase Δ∈.
When X21 and X22 each independently represent a fluorine atom or a hydrogen atom, the following is preferred in order to increase Δ∈:
In order to decrease viscosity,
is preferable.
When X23 to X25 each independently represent a fluorine atom or a hydrogen atom, a choice is preferably made from the following partial structures:
Y21 and Y=22 are particularly preferably a combination selected from a fluorine atom, —CF3, and —OCF3 since the nematic phase lower limit temperature is improved and the low-temperature operation and storage property of the liquid crystal composition are enhanced.
B21 is particularly preferably selected from the following partial structures:
Z21 and Z22 preferably each independently represent a single bond, —CH═CH—, —C≡C—, —CH2CH2—, —(CH2)4—, —OCH2—, —CH2O—, —OCF2—, or —CF2O— and more preferably each independently represent a single bond, —OCH2—, —CH2O—, —OCF2—, or —CF2O—.
Preferably, m21 represents an integer of 0 to 2. When two or more A21 and/or Z21 are present, they may be the same or different.
As the compound represented by general formula (LC2), at least one compound represented by general formula (LC2-a) is preferably contained:
(In the formula, X26 and X27 each independently represent a hydrogen atom or a fluorine atom, Z23 represents —OCH2—, —CH2O—, —OCF2—, or —CF2O—, and R21, A21, Z21, X21, X22, Y21, and m21 are respectively the same as R21, A21, Z21, X21, X22, Y21, and m21 in general formula (LC2).)
X26 and X27 each preferably represent a fluorine atom, at least one of X026 and X27 preferably represents a fluorine atom, and X26 and X27 more preferably both represent a fluorine atom.
The compound represented by general formula (LC2-a) preferably contains at least one compound selected from the compounds represented by general formula (LC2-a1) to general formula (LC2-a11):
(In the formulae, R21, X21, X22, X26, X27, and Y21 are respectively the same as R21, X21, X22, X26, X27, and Y21 in general formula (LC2) and X30, X31, X32, and X33 each independently represent a hydrogen atom or a fluorine atom.) More preferably, at least one selected from the compounds represented by (LC2-a4) to (LC2-a6), (LC2-a10), and (LC2-a11) is contained.
As the compound represented by general formula (LC2), at least one compound represented by general formula (LC2-b) is preferably contained:
(In the formula, R21, A21, A22, X21, X22, Y21, and m21 are respectively the same as R21, A21, A22, X21, X22, Y21, and m21 in general formula (LC2).)
The compound represented by general formula (LC2-b) preferably contains at least one selected from the compounds represented by general formula (LC2-b1) to general formula (LC2-b21):
(In the formula, X34, X35, X36, X37, X38, X39, X50, and X51 each independently represent a hydrogen atom or a fluorine atom and R21, X21, X22, and Y21 are respectively the same as R21, X21, X22, and Y21 in general formula (LC2-b).) More preferably, at least one selected from the compounds represented by general formula (LC2-b5) to general formula (LC2-b8), general formula (LC2-b10) to general formula (LC2-b12), and general formula (LC2-b18) is preferably contained.
As the compound represented by general formula (LC2) other than those represented by general formula (LC2-a) and general formula (LC2-b), the following compounds are preferably contained.
(In the formulae, X40, X41, X42, X43, X44, and X45 each independently represent a hydrogen atom or a fluorine atom and R21, X23, X24, X25, and Y22 are respectively the same as R21, X23, X24, X25, and Y22 in general formula (LC2).)
In the liquid crystal composition according to the present invention, the lower limit of the amount of the compound represented by general formula (LC2) contained is preferably 1% or more, preferably 3% or more, preferably 5% or more, preferably 8% or more, preferably 10% or more, and preferably 15% or more. The upper limit is preferably 50% or less, preferably 45% or less, preferably 40% or less, preferably 35% or less, preferably 30% or less, preferably 25% or less, and preferably 20% or less. The compounds represented by general formula (1) may be used alone or in combination of two or more.
The liquid crystal composition according to the present invention preferably has a viscosity η at 20° C. of 20 mPa·s or less.
The liquid crystal composition according to the present invention can contain at least one optically active compound. Any optically active compound capable of twisting and aligning liquid crystal molecules can be used. Since twisting is usually dependent on the temperature, two or more optically active compounds can be used to obtain a desired temperature dependence. In order to avoid adverse effects on the nematic liquid crystal phase temperature range and viscosity, it is preferable to chose and use an optically active compound having a strong twisting effect. As such an optically active compound, liquid crystals such as cholesteric nonanate and compounds represented by general formula (Ch-1) to general formula (Ch-6) below are preferably contained.
(In the formulae, Rc1, Rc2, and R* each independently represent an alkyl group having 1 to 15 carbon atoms, one or more —CH2— in the alkyl group may each be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF2O—, or —OCF2— so long as oxygen atoms are not directly adjacent to each other, one or more hydrogen atoms in the alkyl group may each be substituted with a halogen, R* has at least one optically active branched chain group or a halogen substituent, Zc1 and Zc2 each independently represent a single bond, —CH═CH—, —C≡C—, —CH2CH2—, —(CH2)4—, —COO—, —OCO—, —OCH2—, —CH2O—, —OCF2—, or —CF2O—, D1 and D2 each represent a cyclohexane ring or a benzene ring, one or more —CH2— in the cyclohexane ring may each be substituted with —O— so long as oxygen atoms are not directly adjacent to each other, one or more —CH2CH2— in the ring may each be substituted with —CH═CH—, —CF2O—, or —OCF2—, one or more —CH═ in the benzene ring may each be substituted with —N═ so long as nitrogen atoms are not directly adjacent to each other, one or more hydrogen atoms in the ring may each be substituted with F, Cl, or CH3, t1 and t2 each represent 0, 1, 2, or 3, and MG*, Qc1, and Qc2 respectively represent the following structures:
(In the formula, D3 and D4 each represent a cyclohexane ring or a benzene ring, one or more —CH2— in the cyclohexane ring may each be substituted with —O— so long as oxygen atoms are not directly adjacent to each other, one or more —CH2CH2— in the ring may each be substituted with —CH═CH—, —CF2O—, or —OCF2—, one or more —CH═ in the benzene ring may each be substituted with —N═ so long as nitrogen atoms are not directly adjacent to each other, and one or more hydrogen atoms in the ring may each be substituted with F, Cl, or CH3.).
The liquid crystal composition according to the present invention may contain at least one polymerizable compound. The polymerizable compound is preferably a discotic liquid crystal compound having a structure in which linear alkyl groups, linear alkoxy groups, or substituted-benzoyloxy groups constitute side chains radially arranged around a core, which is a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative, or a cyclohexane derivative, at the molecular center.
Specifically, the polymerizable compound is preferably represented by general formula (PC):
[Chem. 55]
(P1-Sp1-Qp1p
Rp1)p
(In the formula, P1 represents a polymerizable functional group, Sp1 represents a spacer group having 0 to 20 carbon atoms, Qp1 represents a single bond, —O—, —NH—, —NHCOO—, —OCONH—, —CH═CH—, —CO—, —COO—, —OCO—, —OCOO—, —OOCO—, —CH═CH—, —CH═CH—COO—, —OCO—CH═CH—, or —C≡C—, p1 and p2 each independently represent 1, 2, or 3, MGp represents a mesogen group or a mesogenic support group, Rp1 represents a halogen atom, a cyano group, or an alkyl group having 1 to 25 carbon atoms, and one or more CH2 groups in the alkyl group may each be substituted with —O—, —S—, —NH—, —N(CH3)—, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, or —C≡C— so long as oxygen atoms are not directly adjacent to each other. Alternatively, Rp1 may represent P2-Sp2-Qp2- where P2, Sp2, and Qp2 are respectively the same as P1, Sp1, and Qp1.)
More preferably, the polymerizable compound is one represented by general formula (PC) with MGp representing the following structure:
—C01—Zp1C02—Zp2
p
(In the formula, C01 to C03 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, a 1,3-dioxane-2,5-diyl group, a tetrahydrothiopyran-2,5-diyl group, a 1,4-bicyclo(2,2,2)octylene group, a decahydronaphthalene-2,6-diyl group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a pyrazine-2,5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a 2,6-naphthylene group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7-diyl group, a 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, or a fluorenone 2,7-diyl group, the 1,4-phenylene group, the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the 2,6-naphthylene group, the phenanthrene-2,7-diyl group, the 9,10-dihydrophenanthrene-2,7-diyl group, the 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, and the fluorenone-2,7-diyl group may each have, as a substituent, at least one F, Cl, CF3, OCF3, cyano group, alkyl group having 1 to 8 carbon atoms, alkoxy group, alkanoyl group, alkanoyloxy group, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group, alkenoyl group, or alkenoyloxy group, Zp1 and Zp2 each independently represent —COO—, —OCO—, —CH2CH2—, —OCH2—, —CH2O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH2CH2COO—, —CH2CH2OCO—, —COOCH2CH2—, —OCOCH2CH2—, —CONH—, —NHCO—, or a single bond, and p3 represents 0, 1, or 2.)
Here, when Sp1 and Sp2 each independently represent an alkylene group, that alkylene group may be substituted with one or more halogen atoms or CN and one or more CH2 groups in this group may each be substituted with —O—, —S—, —NH—, —N(CH3)—, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, or —C≡C—so long as oxygen atoms are not directly adjacent to each other. P1 and P2 are each preferably one of the structures represented by the following general formulae:
(In the formulae, Rp2 to Rp6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms.)
Specifically, the polymerizable compound represented by general formula (PC) is preferably selected from polymerizable compounds represented by general formula (PC0-1) to general formula (PC0-6):
[Chem. 58]
(P1-Sp1-Qp1p
Qp2-Sp2-P2)p
(P1-Qp1p
Qp2-P2)p
P1-Sp1-Qp1-MGp-Qp2-Sp2-P2 (PC0-3)
P1-Qp1-MGp-Qp2-P2 (PC0-4)
P1-Sp1-Qp1-MGp-Rp1 (PC0-5)
P1-Qp1-MGp-Rp1 (PC0-6)
(In the formulae, p4 each independently represent 1, 2, or 3.) More specifically, polymerizable compounds represented by general formula (PC1-1) to general formula (PC1-9) are preferable.
(In the formulae, p5 represents 0, 1, 2, 3, or 4.) In particular, Sp1, Sp2, Qp1, and Qp2 preferably each represent a single bond, P1 and P2 are preferably each represented by formula (PC0-a) and more preferably each represent an acryloyloxy group or a methacryloyloxy group, p1+p4 is preferably 2, 3, or 4, and Q preferably represents H, F, CF3, OCF3, CH3, or OCH3. More preferable are compounds represented by general formula (PC1-2), general formula (PC1-3), general formula (PC1-4), and general formula (PC1-8).
Also preferable are discotic liquid crystal compounds represented by general formula (PC) with MGp being represented by general formula (PC1)-9:
(In the formula, R7 each independently represent P1-Sp1-Qp1 or a substituent represented by general formula (PC1-e), R81 and R82 each independently represent a hydrogen atom, a halogen atom, or a methyl group, R83 represents an alkoxy group having 1 to 20 carbon atoms, and at least one hydrogen atom in the alkoxy group is substituted with a substituent represented by any one of general formula (PC0-a) to (PC0-d) described above.)
The amount of the polymerizable compound used is preferably 0.05% to 2.0% by mass.
The liquid crystal composition containing a polymerizable compound according to the present invention is used to prepare a liquid crystal display device by polymerizing the polymerizable compound. During this process, the amount of the unpolymerized components must be decreased to a desired level or lower and thus the compound represented by general formula (LC0) in the liquid crystal composition preferably includes a biphenyl group or a terphenyl group as a partial structure. Specifically, compounds represented by general formula (LC0-10) to general formula (LC0-27), general formula (LC0-48) to general formula (LC0-53), and general formula (LC0-60) to general formula (LC0-68) are preferable and preferably at least one compound is selected from these compounds and contained in an amount of 0.1% to 40% by mass. It is preferable to use a combination of polymerizable compounds selected from those represented by general formula (PC1-1) to general formula (PC1-3), general formula (PC1-8), or general formula (PC1-9).
The liquid crystal composition may further contain one or more antioxidants and one or more UV absorbers. The antioxidants are preferably selected from those represented by general formula (E-1) and/or general formula (E-2) below.
(In the formula, Re1 represents an alkyl group having 1 to 15 carbon atoms, one or more —CH2— in the alkyl group may each be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF2O—, or —OCF2— so long as oxygen atoms are not directly adjacent to each other, one or more hydrogen atoms in the alkyl group may each be substituted with a halogen, Ze1 and Ze2 each independently represent a single bond, —CH═CH—, —C≡C—, —CH2CH2—, —(CH2)4—, —COO—, —OCO—, —OCH2—, —CH2O—, —OCF2—, or —CF2O—,
E1 represents a cyclohexane ring or a benzene ring, one or more —CH2— in the cyclohexane ring may each be substituted with —O— so long as oxygen atoms are not directly adjacent to each other, one or more —CH2CH2— in the ring may each be substituted with —CH═CH—, —CF2O—, or —OCF2—, one or more —CH═ in the benzene ring may each be substituted with —N═ so long as nitrogen atoms are not directly adjacent to each other, at least one hydrogen atom in the ring may be substituted with F, Cl, or CH3, and q1 represents 0, 1, 2, or 3.)
The liquid crystal composition of the present invention can be used in liquid crystal display devices, in particular, active matrix drive liquid crystal display devices of, for example, TN mode, OCB mode, ECB mode, IPS (including FFS electrodes) mode, or VA-IPS mode (including FFS electrodes). Here, the VA-IPS mode refers to a driving mode with which a liquid crystal material having positive dielectric anisotropy (Δ∈>0) is aligned perpendicular to the substrate surface in the absence of applied voltage and liquid crystal molecules are driven by using pixel electrodes and a common electrode disposed on the same substrate surface. Since liquid crystal molecules align in the direction of the bend electric field generated between the pixel electrodes and the common electrode, divided pixels and multi-domains can be easily formed and the response is excellent, which is an advantage. According to Non-Patent Literatures, Proc. 13th IDW, 97 (1997), Proc. 13th IDW, 175 (1997), SID Sym. Digest, 319 (1998), SID Sym. Digest, 838 (1998), SID Sym. Digest, 1085 (1998), SID Sym. Digest, 334 (2000), and Eurodisplay Proc., 142 (2009), various names are used such as EOC and VA-IPS. In the present invention, this mode is simply referred to as “VA-IPS”.
In general, the threshold voltage (Vc) for Fréedericksz transition in TN and ECB mode is given by the following formula:
In IPS mode, it is given by the following formula:
In VA mode, it is given by the following formula:
(In the formula, Vc represents Fréedericksz transition (V), Π represents the circular constant, dcell represents a distance (μm) between a first substrate and a second substrate, dgap represents a distance (μm) between pixel electrodes and a common electrode, dITO represents a width (μm) of the pixel electrodes and/or the common electrode, <r1>, <r2>, and <r3> each represent the extrapolation length (μm), K11 represents the splay elastic constant (N), K22 represents the twist elastic constant (N), K33 represents the bend elastic constant (N), and Δ∈ represents anisotropy of dielectric constant.)
In VA-IPS mode, Mathematical formula 4 below is applied to the present invention and the like.
(In the formula, Vc represents the Fréedericksz transition (V), Π represents the circular constant, dcell represents a distance (μm) between a first substrate and a second substrate, dgap represents a distance (μm) between the pixel electrodes and the common electrode, dITO represents a width (μm) of the pixel electrodes and/or the common electrode, <r>, <r′>, and <r3> each represent an extrapolation length (μm), K33 represents the bend elastic constant (N), and Δ∈ represents anisotropy of dielectric constant.) From Mathematical formula 4, a cell structure can be derived in which low drive voltage can be achieved by decreasing dgap as much as possible and increasing dITO as much as possible and in which low drive voltage can be achieved by choosing and using a liquid crystal composition that has a large absolute value of Δ∈ and a small K33.
A liquid crystal display device prepared by using the liquid crystal composition according to the present invention can be prepared by employing, as a method for aligning the liquid crystal molecules on the substrate surface, a rubbing treatment that uses a polyimide or polyamide compound or the like. It can also be prepared by an optical alignment technique by using a chalcone, cinnamate, or cinnamoyl compound or the like. A new alignment method of incorporating a polymerizable liquid crystal compound into an alignment layer and polymerizing the polymerizable liquid crystal compound can also be applied.
According to the liquid crystal composition of the present invention, Δ∈, K11, K33, etc., can be adjusted to desired values.
The product (Δn·d) of the refractive index anisotropy (Δn) of the liquid crystal composition and the distance (d) between the first substrate and the second substrate of the display device has a strong correlation with the viewing angle properties and response speed. In this respect, the distance (d) tends to be as small as 3 to 4 μm. The product (Δn·d) is particularly preferably 0.31 to 0.33 for the TN, ECB, and IPS (liquid crystal alignment in the absence of voltage application is substantially horizontal to the substrate surface) modes. In the VA-IPS mode, the product is preferably 0.20 to 0.59 and particularly preferably 0.30 to 0.40 when the alignment is vertical to the two substrates. Since the optimum value of the product (Δn·d) differs depending on the mode of the display device, the refractive index anisotropy (Δn) of the liquid crystal composition suitable for various modes is in the range of 0.070 to 0.110, 0.100 to 0.140, or 0.130 to 0.180. A liquid crystal composition having a refractive index anisotropy (Δn) in any of various different ranges can be prepared.
The liquid crystal composition according to the present invention, which contains a compound represented by general formula (PC) as a polymerizable compound, can offer a polymer-stabilized TN-mode, OCB-mode, ECB-mode, IPS-mode or VA-IPS mode liquid crystal display device prepared by polymerizing the polymerizable compound contained in the liquid crystal composition in the presence or absence of the applied voltage. Specifically, the liquid crystal composition containing a polymerizable compound is interposed between the two substrates and the polymerizable compound in the liquid crystal composition is polymerized through energy such as UV light in the presence or absence of the applied voltage. With this liquid crystal display device, the alignment state of the liquid crystal molecules can be memorized by polymerizing the polymerizable compound and thus the stability of the alignment state can be improved. The response speed can also be expected to improve.
The present invention will now be described in further detail through examples below which do not limit the scope of the present invention. In Examples and Comparative Examples below, “%” associated with the compositions means % by mass.
The physical properties of the liquid crystal composition are denoted as follows.
TN-I: nematic phase-isotropic liquid phase transition temperature (° C.)
T-n: nematic phase lower limit temperature (° C.)
∈⊥: dielectric constant in a direction perpendicular to a molecular long axis at 25° C.
Δ∈: dielectric anisotropy at 25° C.
no: refractive index for ordinary light at 25° C.
Δn: refractive index anisotropy at 25° C.
Vth: applied voltage (V) of a 6 μm-thick cell whose transmittance changed by 10% when square waves at a frequency of 1 KHz were applied at 25° C.
η: bulk viscosity at 20° C. (mPa·s)
γ1: rotational viscosity (mPa·s)
The following abbreviations are used to describe compounds.
The measured properties of the liquid crystal compositions stored at −20° C., −25° C., −30° C., and −40° C. are indicated in the table. In the table, numerals indicate the storage time, A indicates that the sample after the storage time maintained a liquid crystal state similar to one before storage, and F indicates that precipitation occurred during the storage time.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
Comparative Examples were prepared so that the nematic phase-isotropic liquid phase transition temperature (TN-I) and the value of the dielectric anisotropy (Δ∈) at 25° C. were about the same level as those of Examples. Whereas η in Examples 1 to 6 was in the range of 13.7 mPa·s to 14.7 mPa·s, η in Comparative Examples 1 and 2 was 18.4 mPa·s and 18.5 mPa·s, respectively. Whereas γ1 in Examples 1 to 6 was in the range of 68 mPa·s to 79 mPa·s, γ1 in Comparative Examples 1 and 2 was 94 Pa-s and 87 Pa-s, respectively. In the liquid crystal compositions of Examples 4 and 5, precipitation was not observed after 168 hours of storage at −30° C. and excellent low-temperature phase stability was confirmed. However, in the liquid crystal compositions of Comparative Examples 1 and 2, precipitation was observed after 72 hours at −30° C.
The results show that the liquid crystal compositions of Examples 1 to 6 in which a compound represented by general formula (LC0) was used according to the subject application exhibited significantly lower γ1 and excellent low-temperature storage property compared to the liquid crystal compositions of Comparative Examples 1 and 2 in which no compound represented by general formula (LC0) was used.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
The liquid crystal compositions prepared and their physical properties are shown below.
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