Patent Application
20180346614
The present invention relates to a polymer having optical anisotropy that requires various optical characteristics, a polymerizable composition which is useful as a constituent member of a film, an optically anisotropic body, a retardation film, an optical compensation film, an anti-reflective film, a lens, and a lens sheet which are famed of the polymerizable composition, a liquid crystal display element, an organic light-emitting display element, a lighting element, an optical component, a polarizing film, a colorant, a security marking, a member for emitting a laser, and a printed matter for which the polymerizable composition is used.
A compound (polymerizable compound) containing a polymerizable group is used for various optical materials. For example, a uniformly aligned polymer can be prepared by aligning a polymerizable composition containing a polymerizable compound in a liquid crystal state and then polymerizing the aligned composition. Such a polymer can be used for a polarizing plate, a retardation plate, and the like which are required for a display. In many cases, a polymerizable composition containing two or more polymerizable compounds is used to satisfy optical characteristics, the polymerization rate, the solubility, the melting point, the glass transition temperature, the transparency of the polymer, the mechanical strength, the surface hardness, the heat resistance, and the light resistance to be required. At this time, it is necessary that the polymerizable compounds to be used provide excellent physical properties for the polymerizable composition without adversely affecting other characteristics.
For improving the view angle of a liquid crystal display, or as a retardation film for a circularly-polarizing plate for use as an antireflection film for OLED, wavelength dispersion of birefringence is required to lower or reverse. As a material for that purpose, various polymerizable compositions having reverse wavelength dispersion or low wavelength dispersion have been developed. However, such polymerizable compositions often cause crystal precipitation and the storage stability thereof is insufficient (PTL 1). In addition, when the polymerizable composition is applied to a substrate and polymerized thereon, there occurs a problem of unevenness in coating (PTL 1 to PTL 3). In the case where such an unevenly-coated film is used in, for example, an display, there occur problems in that the brightness of the screen may be uneven or the color thereof may be unnatural so that the quality of the display products may be greatly worsened. Accordingly, development of a polymerizable composition having reverse wavelength dispersion or low wavelength dispersion and capable of solving these problems is desired. For solving the problem of unevenness, in general, some surfactant may be added to a polymerizable composition (PTLs 2 to 5), which, however, is problematic in that, when the polymerizable composition is applied to a substrate and then polymerized thereon and when the coated substrates are kept in contact with each other by stacking them, the surfactant existing in the coated surface may undergo offset to the neighboring substrate to cause appearance failure. Further, depending on the combination of the polymerizable composition and a surfactant, there may occur a probability of cissing. Consequently, for simultaneously solving the previous problems of coating unevenness and cissing and the problem of offset, optimum selection of surfactant is now an important technique.
PTL 1: JP-2008-107767A
PTL 2: JP-2010-522892A
PTL 3: JP-2013-509458A
PTL 4: WO12/147904A1
PTL 5: JP-2009-062508A
An object of the present invention is to provide a polymerizable composition excellent in solubility and having high storage stability not causing crystal precipitation or the like, and to provide a polymerizable composition which has, when formed into a filmy polymer through polymerization of the composition, excellent aligning performance and leveling performance, which hardly causes defects, unevenness and cissing, and which hardly causes appearance failure owing to surfactant offset. Further, the present invention is to provide a polymer, an optically anisotropic body, a display element, a light-emitting element and the like using the polymerizable composition.
For solving the above-mentioned problems, the present inventors have made assiduous studies taking particular note of a polymerizable compound having a specific structure having one polymerizable group or two or more polymerizable groups and a polymerizable composition using a specific surfactant, and provide here the present invention.
Specifically, the present invention provides:
a polymerizable composition containing:
a) one or two or more polymerizable compounds each having one polymerizable group or two or more polymerizable groups and satisfying a formula (I):
Re(450 nm)/Re(550 nm)<1.0 (I)
(wherein Re(450 nm) represents an in-plane phase difference of the polymerizable compound containing one polymerizable group at a wavelength of 450 nm in the case where the molecules of the compound are aligned on a substrate such that a longitudinal axis direction of each molecule is aligned substantially horizontally with respect to the substrate, and Re(550 nm) represents an in-plane phase difference of the polymerizable compound containing one polymerizable group at a wavelength of 550 nm in the case where the molecules of the compound are aligned on a substrate such that a longitudinal axis direction of each molecule is aligned substantially horizontally with respect to the substrate), and
b) one or two or more compounds represented by a general formula (B):
[Chem. 1]
(R71n
(wherein MG1 represents a mesogen group, R71 and R72 each represent an alkyl group having 4 to 30 carbon atoms, 4 or more hydrogen atoms in R71 and R72 are substituted with fluorine atoms, and one or more (—CH2—)'s therein may be substituted with an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —COS—, or —SCO—, and n81 and n82 each represent a positive integer, provided that n81+n82 represents an integer of 2 to 6).
In addition, the invention provides a polymer, an optically anisotropic body, a display element, a light-emitting element and the like using the polymerizable composition.
The polymerizable composition of the present invention simultaneously uses a polymerizable compound having a specific structure having one polymerizable group or two or more polymerizable groups and having reverse wavelength dispersion, and a specific surfactant, and therefore, it is possible to obtain a polymerizable composition excellent in solubility and storage stability. In addition, it is possible to obtain a polymer, an optically anisotropic body, a retardation film and the like excellent in leveling performance of the coated surface, having low risk of offset from the liquid crystal-coated surface and excellent in productivity.
Hereinafter, the best mode of a polymerizable composition according to the present invention will be described. In the present invention, the “liquid crystalline compound” is intended to refer to a compound having a mesogenic skeleton, which is a rigid skeleton with which liquid crystallinity may be exhibited, and the compound alone does not need to exhibit liquid crystallinity.
Further, the polymerizable compound can be made into a polymer (or a film) by performing a polymerization treatment by means of irradiating the polymerizable composition with light such as ultraviolet rays or heating the polymerizable composition.
The birefringence of the liquid crystalline compound containing one or two or more polymerizable groups of the present invention is larger on a long wavelength side than on a short wavelength side in a visible light region. Specifically, insofar as the liquid crystalline compound containing one or two or more polymerizable group satisfies Formula (I), the birefringence thereof does not need to be larger on a long wavelength side than on a short wavelength side in an ultraviolet region or an infrared region.
Re(450 nm)/Re(550 nm)<1.0 (I)
(In the formula, Re(450 nm) represents an in-plane phase difference of the polymerizable compound containing one polymerizable group at a wavelength of 450 nm in the case where the molecules of the compound are aligned on a substrate such that a longitudinal axis direction of each molecule is aligned substantially horizontally with respect to the substrate, and Re(550 nm) represents an in-plane phase difference of the polymerizable compound containing one polymerizable group at a wavelength of 550 nm in the case where the molecules of the compound are aligned on a substrate such that a longitudinal axis direction of each molecule is aligned substantially horizontally with respect to the substrate.)
The compound is preferably a liquid crystalline compound. The compound preferably includes at least one liquid crystalline compound selected from the group consisting of liquid crystalline compounds represented by any one of General Formulae (1) to (7).
In the formulae, P11 to P74 represent a polymerizable group, S11 to S72 represent a spacer group or a single bond, and in the case where plural groups are present with respect to each of S11 to S72, these may be the same as or different from each other.
X11 to X72 represent —O—, —S—, —OCH2—, —CH2O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH, —N═N—, CH═N N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where plural groups are present with respect to each of X11 to X72, these may be the same as or different from each other, provided that each of P—(S—X)— bonds does not have —O—O—, —S—S—, —S—O—, and —O—S—.
MG11 to MG71 each independently represent formula (a):
(In the formula, A11 and A12 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group, these groups may be unsubstituted or substituted with one or more L1's, and in the case where plural groups are present with respect to each of A11 and A12, these may be the same as or different from each other.
Z11 and Z12 each independently represent —O—, —S—, —OCH2—, —CH2O—, —CH2CH2—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH, —N═N—, CH═N, —N═CH—, CH═N—N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where plural groups are present with respect to each of Z11 and Z12, these may be the same as or different from each other.
M represents a group selected from groups represented by Formula (M-1) to Formula (M-11), and these groups may be unsubstituted or substituted with one or more L1's:
G represents a group selected from groups represented by Formula (G-1) to Formula (G-6):
(In the formulae, R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O, —CO—NH—, —NH—CO—, or —C≡C—;
W81 represents a group having at least one aromatic group and 5 to 30 carbon atoms and the group may be unsubstituted or substituted with one or more L1's;
W82 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom and/or —OH, one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, W82 may have the same definition as that for W81, W81 and W82 may be linked to each other to form the same ring structure, or W82 may represent a group represented by P8—(S8—X8)j—, where P8 represents a polymerizable group, S8 represents a spacer group or a single bond, and in case where a plurality of S8's are present, these may be the same as or different from each other, X8 represents —O—, —S—, —OCH2—, —CH2O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where a plurality of X8's are present, these may be the same as or different from each other, provided that P8—(S8—X8)j— bonds does not have —O—O—, and j represents an integer of 0 to 10; and
W83 and W84 each independently represent a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, a group having at least one aromatic group and 5 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, or an alkylcarbonyloxy group having 2 to 20 carbon atoms, one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkoxy group, the acyloxy group, and the alkylcarbonyloxy group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O, —CO—NH—, —NH—CO—, or —C≡C—, provided that G represents a group selected from groups represented by Formula (G-1) to Formula (G-5) in the case where M represents a group selected from groups represented by Formula (M-1) to Formula (M-10) and G represents a group represented by Formula (G-6) in the case where M represents a group represented by Formula (M-11).)
L1 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxy group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms may be substituted with a fluorine atom, one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with a group selected from —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—OCO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, and in the case where a plurality of L1's are present in the compound, these may be the same as or different from each other.
j11 represents an integer of 1 to 5, and j12 represents an integer of 1 to 5, provided that j11+j12 represents an integer of 2 to 5.)
R11 and R31 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, m11 represents an integer of 0 to 8, and m2 to m7, n2 to n7, 14 to 16, and k6 each independently represent an integer of 0 to 5.
In General Formula (1) to General Formula (7), it is preferable that polymerizable groups P11 to P74 represent a group selected from groups represented by any of Formulae (P-1) to (P-20) and these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization.
Particularly, in the case where ultraviolet polymerization is performed as a polymerization method, Formula (P-1), Formula (P-2), Formula (P-3), Formula (P-4), Formula (P-5), Formula (P-7), Formula (P-11), Formula (P-13), Formula (P-15), or Formula (P-18) is preferable, Formula (P-1), Formula (P-2), Formula (P-7), Formula (P-11), or Formula (P-13) is more preferable, Formula (P-1), Formula (P-2), or Formula (P-3) is still more preferable, and Formula (P-1) or Formula (P-2) is particularly preferable.
In General Formula (1) to General Formula (7), S11 to S72 represent a spacer group or a single bond, and in the case where plural groups are present with respect to each of S11 to S72, these may be the same as or different from each other. Further, it is preferable that the spacer group is an alkylene group having 1 to 20 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —COO—, —OCO—, —OCO—O—, —CO—NH—, —NH—CO—, —CH═CH—, —C≡C—, or the following Formula (S-1).
From the viewpoints of easily obtaining raw materials and ease of synthesis, it is more preferable that S11 to S72 each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —COO—, or —OCO— in the case where a plurality of S's are present, these may be the same as or different from each other, it is still more preferable that S each independently represent an alkylene group having 1 to 10 carbon atoms or a single bond, and it is particularly preferable that S each independently represent an alkylene group having 1 to 8 carbon atoms, in the case where a plurality of S's are present, these may be the same as or different from each other.
In General Formula (1) to General Formula (7), X11 to X72 represent —O—, —S—, —OCH2—, —CH2O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where plural groups are present with respect to each of X11 to X72, these may be the same as or different from each other, provided that P—(S—X)— bond does not have a —O—O— bond.
From the viewpoints of easily obtaining raw materials and ease of synthesis, it is preferable that X11's to X72's each independently represent —O—, —S—, —OCH2—, —CH2O—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, or a single bond in the case where plural groups are present with respect to each of X11 to X72 are present, these may be the same as or different from each other, it is more preferable that X11's to X72's each independently represent —O—, —OCH2—, —CH2O—, —COO—, —OCO—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, or a single bond, and it is particularly preferable that X11's to X72's each independently represent —O—, —COO—, —OCO—, or a single bond, in the case where plural groups are present with respect to each of X11 to X72, these may be the same as or different from each other.
In General Formula (1) to General Formula (7), A11 and A12 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group, these groups may be unsubstituted or substituted with one or more L's, and in the case where plural groups are present with respect to each of A11 and A12, these may be the same as or different from each other.
From the viewpoints of easily obtaining raw materials and ease of synthesis, it is preferable that A11 and A12 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, or a naphthalene-2,6-diyl which may be unsubstituted or substituted with one or more L1's, more preferable that A11 and A12 each independently represent a group selected from groups represented by Formula (A-1) to Formula (A-11), still more preferable that A1 and A12 each independently represent a group selected from groups represented by Formula (A-1) to Formula (A-8), and particularly preferable that A11 and A12 each independently represent a group selected from groups represented by Formula (A-1) to Formula (A-4).
In General Formula (1) to General Formula (7), Z11 and Z12 each independently represent —O—, —S—, —OCH2—, —CH2O—, —CH2CH2—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —OCO—NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH—, —N═N—, —CH═N—, —N═CH—, —CH═N—N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where plural groups are present with respect to each of Z11 and Z12, these may be the same as or different from each other.
From the viewpoints of liquid crystallinity of compounds, easily obtaining raw materials, and ease of synthesis, it is preferable that Z11 and Z12 each independently represent a single bond, —OCH2—, —CH2O—, —COO—, —OCO—, —CF2O—, —OCF2—, —CH2CH2—, —CF2CF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —CH═CH—, —CF═CF—, —C≡C—, or a single bond, it is more preferable that Z11 and Z12 each independently represent —OCH2—, —CH2O—, —CH2CH2—, —COO—, —OCO—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —CH═CH—, —C≡C—, or a single bond, it is still more preferable that Z11 and Z12 each independently represent —OCH2—, —CH2O—, —CH2CH2—, —COO—, —OCO—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, or a single bond, and it is particularly preferable that Z11 and Z12 each independently represent —CH2CH2—, —COO—, —OCO—, or a single bond.
In General Formula (1) to General Formula (7), M represents a group selected from groups represented by Formula (M-1) to Formula (M-11), and these groups may be unsubstituted or substituted with one or more L1's.
From the viewpoints of easily obtaining raw materials and ease of synthesis, it is preferable that M's each independently represent a group selected from groups represented by Formula (M-1) and Formula (M-2) which may be unsubstituted or substituted with one or more L1's or Formula (M-3) to Formula (M-6) which are unsubstituted, it is more preferable that M's each independently represent a group selected from groups represented by Formula (M-1) and Formula (M-2) which may be unsubstituted or substituted with one or more L1's, and it is particularly preferable that M's each independently represent a group selected from groups represented by Formula (M-1) and Formula (M-2) which are unsubstituted.
In General Formula (1) to General Formula (7), R11 and R31 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, and one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom. From the viewpoint of liquid crystallinity and ease of synthesis, it is preferable that R11 and R31 represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —COO—, —OCO—, or —O—CO—O—, it is more preferable that R1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms, and it is particularly preferable that R1 represents a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms.
In General Formula (1) to General Formula (7), G represents a group selected from groups represented by Formula (G-1) to Formula (G-6).
In the formulae, R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—,
W81 represents a group having at least one aromatic group and 5 to 30 carbon atoms and the group may be unsubstituted or substituted with one or more L1's, and
W82 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom and/or —OH, and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, W82 may have the same definition as that for W81, or W82 may represent a group represented by P8—(S8—X8)j—, where P8 represents a polymerizable group, S8 represents a spacer group or a single bond, and in case where a plurality of S8's are present, these may be the same as or different from each other, X8 represents —O—, —S—, —OCH2—, —CH2O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where a plurality of X8's are present, these may be the same as or different from each other, provided that P8—(S8—X8)j— bonds does not have —O—O—, and j represents an integer of 0 to 10, and W81 and W82 may be linked to each other to form a ring structure.
The aromatic group included in the group as W81 may be an aromatic hydrocarbon group or an aromatic heterocyclic group and the group may include both of an aromatic hydrocarbon group and an aromatic heterocyclic group. These aromatic groups may be bonded to each other through a single bond or a linking group (—OCO—, —COO—, —CO—, —O—) and may form a fused ring. Further, in addition to an aromatic group, the group as W81 may further have an acyclic structure and/or a cyclic structure other than aromatic group. From the viewpoints of easily obtaining raw materials and ease of synthesis, the aromatic group included in the group as W81 is a group represented by any of Formulae (W-1) to (W-19) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position, a group formed by linking two or more aromatic groups selected from these groups with a single bond may be formed, and Q1 represents —O—, —S—, —NR4— (where R4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), or —CO—. (—CH═)'s in these aromatic groups may be each independently substituted with —N═, (—CH2—)'s may be each independently substituted with —O—, —S—, —NR4— (where R4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), or —CO—, provided that a —O—O— bond is not formed.) It is preferable that the group represented by Formula (W-1) is a group selected from groups represented by Formula (W-1-1) to Formula (W-1-8) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position.) It is preferable that the group represented by Formula (W-7) is a group selected from groups represented by Formula (W-7-1) to Formula (W-7-7) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position.) It is preferable that the group represented by Formula (W-10) is a group selected from groups represented by Formula (W-10-1) to Formula (W-10-8) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable that the group represented by Formula (W-11) is a group selected from groups represented by Formula (W-11-1) to Formula (W-11-13) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable that the group represented by Formula (W-12) is a group selected from groups represented by Formula (W-12-1) to Formula (W-12-19) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position, R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and in the case where, a plurality of R6 are present, these may be the same as or different from each other.) It is preferable that the group represented by Formula (W-13) is a group selected from groups represented by Formula (W-13-1) to Formula (W-13-10) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and in the case where, a plurality of R6 are present, these may be the same as or different from each other.) It is preferable that the group represented by Formula (W-14) is a group selected from groups represented by Formula (W-14-1) to Formula (W-14-4) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable that the group represented by Formula (W-15) is a group selected from groups represented by Formula (W-15-1) to Formula (W-15-18) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable that the group represented by Formula (W-16) is a group selected from groups represented by Formula (W-16-1) to Formula (W-16-4) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable that the group represented by Formula (W-17) is a group selected from groups represented by Formulae (W-17-1) to (W-17-6) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable that the group represented by Formula (W-18) is a group selected from groups represented by Formula (W-18-1) to Formula (W-18-6) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and in the case where a plurality of R6's are present, these may be the same as or different from each other.) It is preferable that the group represented by Formula (W-19) is a group selected from groups represented by Formula (W-19-1) to Formula (W-19-9) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, these groups may have a binding site at an arbitrary position and R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and in the case where a plurality of R6's are present, these may be the same as or different from each other.) It is more preferable that the aromatic group included in the group represented by W81 is a group selected from groups represented by Formulae (W-1-1), (W-7-1), (W-7-2), (W-7-7), (W-8), (W-10-6), (W-10-7), (W-10-8), (W-11-8), (W-11-9), (W-11-10), (W-11-11), (W-11-12), and (W-11-13) which may be unsubstituted or substituted with one or more L1's and it is particularly preferable that the aromatic group included in the group represented by W81 is a group selected from groups represented by Formulae (W-1-1), (W-7-1), (W-7-2), (W-7-7), (W-10-6), (W-10-7), and (W-10-8) which may be unsubstituted or substituted with one or more L1's. Further, it is particularly preferable that W81 represents a group selected from groups represented by Formulae (W-a-1) to (W-a-6).
(In the formulae, r represents an integer of 0 to 5, s represents an integer of 0 to 4, and t represents an integer of 0 to 3.)
W82 represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom, W82 may have the same definition as that for W81, W81 and W82 may be linked to each other to form a ring structure.
From the viewpoints of easily obtaining raw materials and ease of synthesis, it is preferable that W82 represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms in which one or more of arbitrary hydrogen atoms may be substituted with a fluorine atom and/or —OH and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, or W82 represents a group represented by P8—(S8—X8)j—, it is more preferable that W82 represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms in which one or more of arbitrary hydrogen atoms may be substituted with a fluorine atom and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —CO—, —COO—, or —OCO—, or W82 represents a group represented by P8—(S8—X8)j—, it is still more preferable that W82 represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, or W82 represents a group represented by P8—(S8—X8)j—, and it is still more preferable that W82 represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, or W82 represents a group represented by P8—(S8—X8)j—.
Further, in the case where W82 represents a group having at least one aromatic group and 2 to 30 carbon atoms, W82 preferably represents a group selected from Formula (W-1) to Formula (W-18). In that case, a more preferable structure is the same as the above.
Further, in the case where W82 is a group represented by P8—(S8—X8)_—, preferable structures of groups represented by P8, S8, and X8 are the same as those of the groups represented by P11 to P74, S11 to S72, and X11 to X72, respectively. j is preferably an integer of 0 to 3, and more preferably 0 or 1. A terminal group of W82 may be a OH group.
Further, in the case where W81 and W82 are linked to each other to form a ring structure, it is preferable that the cyclic group represented by —NW81W82 is a group selected from groups represented by Formulae (W-b-1) to (W-b-42) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) From the viewpoints of easily obtaining raw materials and ease of synthesis, it is particularly preferable that the cyclic group represented by —NW81W82 is a group selected from groups represented by Formulae (W-b-20), (W-b-21), (W-b-22), (W-b-23), (W-b-24), (W-b-25), and (W-b-33) which may be unsubstituted or substituted with one or more L1's.
Further, it is preferable that the cyclic group represented by ═CW81W82 is a group selected from groups represented by Formulae (W-c-1) to (W-c-81) which may be unsubstituted or substituted with one or more L1's.
(In the formulae, R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and in the case where, a plurality of R6 are present, these may be the same as or different from each other.) From the viewpoints of easily obtaining raw materials and ease of synthesis, it is particularly preferable that the cyclic group represented by ═CW81W82 is a group selected from groups represented by Formulae (W-c-11), (W-c-12), (W-c-13), (W-c-14), (W-c-53), (W-c-54), (W-c-55), (W-c-56), (W-c-57), and (W-c-78) which may be unsubstituted or substituted with one or more L's.
The total number of π electrons included in the group represented by W81 and W82 is preferably 4 to 24 from the viewpoints of wavelength dispersion characteristics, storage stability, liquid crystallinity, and ease of synthesis. W83 and W84 each independently represent a group selected from a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, a group having at least one aromatic group and 5 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyoxy group having 2 to 20 carbon atoms, or an alkylcarbonyloxy group having 2 to 20 carbon atoms and, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkoxy group, the acyloxy group and the alkylcarbonyloxy group, in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may each independently be substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—. It is more preferable that W83 represents a group selected from a cyano group, a nitro group, a carboxyl group, and an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group, and an alkylcarbonyloxy group, in which one —CH2— or two or more (—CH2—)'s that are not adjacent to each other, may each independently be substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, it is particularly preferable that W83 represents a group selected from a cyano group, a carboxyl group, and an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group, and an alkylcarbonyloxy group, in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may each be independently substituted with —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—. It is more preferable that W84 represents a group selected from a cyano group, a nitro group, a carboxyl group, and an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group, and an alkylcarbonyloxy group, in which one —CH2— or two or more (—CH2—)'s that are not adjacent to each other may each independently be substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, it is particularly preferable that W84 represents a group selected from a cyano group, a carboxyl group, and an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group, and an alkylcarbonyloxy group, in which one —CH2— or two or more (—CH2—)'s that are not adjacent to each other may each be independently substituted with —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—.
L1 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxy group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, and one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom.
From the viewpoints of liquid crystallinity and ease of synthesis, it is preferable that L represents a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or a linear or branched alkyl group having 1 to 20 carbon atoms in which one or more of arbitrary hydrogen atoms may be substituted with a fluorine atom and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with a group selected from —O—, —S—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—, —CF═CF—, and —C≡C—, it is more preferable that that L represents a fluorine atom, a chlorine atom, or a linear or branched alkyl group having 1 to 12 carbon atoms in which one or more of arbitrary hydrogen atoms may be substituted with a fluorine atom and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with a group selected from —O—, —COO—, and —OCO—, it is still more preferable that L represents a fluorine atom, a chlorine atom, or a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms in which one or more of arbitrary hydrogen atoms may be substituted with a fluorine atom, and it is particularly preferable that L represents a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms. In General Formula (1) to General Formula (7), substituents bonded to MG1 to MG71 are bonded to A11 and/or A12 in General Formula (a).
In General Formula (1), m11 represents an integer of 0 to 8. From the viewpoints of liquid crystallinity, easily obtaining raw materials, and ease of synthesis, m11 represents preferably an integer of 0 to 4, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.
In General Formula (2) to General formula (7), m2 to m7, n2 to n7, 14 to 16, and k6 each independently represent an integer of 0 to 5. From the viewpoints of liquid crystallinity, easily obtaining raw materials, and ease of synthesis, m2 to m7, n2 to n7, 14 to 16, and k6 represent preferably an integer of 0 to 4, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.
In General Formula (a), j11 and J12 each independently represent an integer of 1 to 5, provided that j11+j12 represents an integer of 2 to 5. From the viewpoints of liquid crystallinity, ease of synthesis, and storage stability, j11 and j12 each independently represent preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. It is preferable that j11+j12 represents an integer of 2 to 4.
Preferred specific examples of the compound represented by General Formula (1) include compounds represented by Formula (1-a-1) to Formula (1-a-93).
These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (2) include compounds represented by Formula (2-a-1) to Formula (2-a-69).
(In the formulae, n represents an integer of 1 to 10.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (3) include compounds represented by Formula (3-a-1) to Formula (3-a-17).
These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (4) include compounds represented by Formula (4-a-1) to Formula (4-a-26).
(In the formulae, m and n each independently represent an integer of 1 to 10.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (5) include compounds represented by Formula (5-a-1) to Formula (5-a-29).
(In the formulae, n represents 1 to 10 in terms of a carbon atom number.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (6) include compounds represented by Formula (6-a-1) to Formula (6-a-25).
(In the formulae, k, 1, m and n each independently represent 1 to 10 in terms of carbon atom number.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (7) include compounds represented by Formula (7-a-1) to Formula (7-a-26).
These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
The total content of the polymerizable compound having one or two or more polymerizable groups is preferably 60 to 100% by mass relative to the total amount of the polymerizable compounds used in the polymerizable composition, more preferably 65 to 98% by mass, even more preferably 70 to 95% by mass.
The polymerizable composition of the present invention contains one or two or more compounds represented by the general formula (B).
[Chem. 99]
(R71n
(In the formula, MG1 represents a mesogen group, R71 and R72 each represent an alkyl group having 4 to 30 carbon atoms, 4 or more hydrogen atoms in R71 and R72 are substituted with fluorine atoms, and one or more (—CH2—)'s therein may be substituted with an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —COS—, or —SCO—, and n81 and n82 each represent a positive integer, provided that n81+n82 represents an integer of 2 to 6.)
MG1 represents a mesogen group, and preferably has a structure represented by formulae (B-1) to (B-3).
(In the formulae, A71, A72 and A73 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 pyrrole-2,5-diyl group, a thiophene-2,5-diyl group, a furan-2,5-diyl group, a fluorene-2,7-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, a 1,4-naphthylene group, a benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl group, a benzo[1,2-b:4,5-b′]diselenophene-2,6-diyl group, a [1]benzothieno[3,2-b]thiophene-2,7-diyl group, a [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or a fluorene-2,7-diyl group, and each may have one or more substituents selected from F, Cl, CF3, OCF3, CN, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, an alkenoyloxy group having 2 to 8 carbon atoms, and R71 and R72 defined in the general formula (B),
Z71 and Z72 each independently represent —COO—, —OCO—, —CH2CH2—, —OCH2—, —CH2O—, —CH═CH—, —N═N—, —C═N—N═C—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH2CH2COO—, —CH2CH2OCO—, —COOCH2CH2—, —OCOCH2CH2—, —C═N—, —N═C—, —CONH—, —NHCO—, —C(CF3)2—, an alkylene group having 2 to 10 carbon atoms and optionally having a halogen atom, or a single bond,
m81 represents an integer of 0 to 2,
X81 to X89 each independently represent a single bond, an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, —NH—, an alkylene group having 1 to 10 carbon atoms (in which one or more (CH2)'s existing in the alkylene group may be each mutually independently substituted with —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, —CH═CH— or —C≡C—, provided that oxygen atoms do not mutually directly bond to each other, sulfur atoms do not mutually directly bond to each other, and an oxygen atom and a sulfur atom do not mutually directly bond to each other), and
A81 to A83 each independently represent a single bond, a 1,4-phenylene group, a 1,3-phenylene group.)
The compound represented by the general formula (B) segregates on the surface of the polymerizable composition and controls the alignment state in the air interface of the liquid-crystalline compound represented by the general formulae (1) to (7) while improving the leveling performance in the interface. In the case of a liquid crystal composition containing a liquid-crystalline compound where the compound represented by the general formula (B) exists in the composition, the compound is a factor to disturb an alignment state. Consequently, the segregation degree is preferably higher, but all do not always segregate and a part of the compounds may remain in the composition. Accordingly, the compound of the general formula (B) preferably has a liquid crystal skeleton since the compound of the type may hardly disturb an alignment state.
MG1 in the general formula (B) is preferably the formula (B-1) among the formulae (B-1) to (B-3).
Preferably, A71, A72 and A73 in the formula (B-1) each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 2,6-naphthylene group, a fluorene-2,7-diyl group, a phenanthrene-2,7-diyl group (optionally having one or more substituents of F, Cl, CF3, OCF3, CN, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and R71 and R72 defined in the general formula (B)), more preferably a 1,4-phenylene group, a 1,4-cyclohexylene group (optionally having one or more substituents of F, a methyl group, a methoxy group, and R71 and R72 defined in the general formula (B)); preferably, Z71 and Z72 are each independently —COO—, —OCO—, —CH2CH2—, or a single bond, more preferably —COO— or —OCO—; preferably, n81 and n82 each are a positive integer, and n81+n82 is an integer of 2 to 4, and more preferably, n81=1, and n82=1.
Preferably, X81 to X83 in (B-2) are each independently —COO—, —OCO—, or —NH—; and preferably, A81 to A83 are each independently a 1-4-phenylene group.
Preferably, X84 to X89 in (B-3) are each independently an oxygen atom, —COO— or —OCO—.
Specifically, compounds represented by the following formulae (B-1-1) to (B-1-71), (B-1-101) to (B-1-132), (B-2-1), (B-2-2), (B-3-1) and (B-3-2) are preferred.
The content of the compound represented by the general formula (B) is preferably 0.01% by mass to 2.0% by mass relative to the total amount of the polymerizable compounds, more preferably 0.02% by mass to 1.0% by mass, even more preferably 0.03% by mass to 0.5% by mass, and most preferably 0.05% by mass to 0.3% by mass.
On the other hand, too much segregation of the compound of the general formula (B) may cause cissing. To evade this, the viscosity of the liquid crystal composition is preferably higher, and the viscosity thereof at 80° C. is preferably 10 Pa·s or more, the viscosity thereof at 80° C. is more preferably 100 Pa·s or more, the viscosity thereof at 80° C. is even more preferably 500 Pa·s or more, and the viscosity thereof at 80° C. is further more preferably 1,000 Pa·s or more. However, when the viscosity thereof is too high, the liquid crystal composition could hardly undergo alignment, and therefore, the viscosity is preferably 10,000,000 Pa·s or less, more preferably 1,000,000 Pa·s or less, even more preferably 100,000 Pa·s or less.
The viscosity is measured using a rheometer Physica MCR101 (manufactured by Anton Paar Corporation) with Corn Plate CP50-1 under the condition of a temperature of 80° C. and a rotation number of 1 rpm. For those that could not be measured at 80° C., the values measured at any other temperature at plural sites were applied to the Andrade viscosity expression to calculate the viscosity of the composition.
(Polymerization Initiator)
The polymerizable composition of the present invention may contain an initiator as necessary. A polymerization initiator used in the polymerizable composition of the present invention is used for polymerizing the polymerizable composition of the present invention. A photopolymerization initiator used in the case where the polymerization is performed by irradiation with light is not particularly limited, and conventionally known initiators can be used to the extent that does not inhibit the alignment state of the polymerizable composition of the present invention.
Examples of the conventionally known initiators include 1-hydroxycyclohexylphenylketone “IRGACURE 184”, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one “DAROCURE 1116”, 2-methyl-1-[(methylthio)phenyl]-2-morpholinopropane-1 “IRGACURE 907”, 2,2-dimethoxy-1,2-diphenylethane-1-one “IRGACURE 651”, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone “IRGACURE 369”, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-phenyl) butane-1-one “IRGACURE 379”, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide “LUCIRIN TPO”, 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide “IRGACURE 819”, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone “IRGACURE OXE01”, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime)“IRGACURE OXE02” (all manufactured by BASF SE), a mixture of 2,4-diethylthioxanthone (“KAYACURE DETX”, manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylamino benzoate (“KAYACURE EPA”, manufactured by Nippon Kayaku Co., Ltd.), a mixture of isopropylthioxanthone (“QUANTACURE ITX”, manufactured by Ward Blenkinsop Co., Ltd.) and ethyl p-dimethylamino benzoate, “ESACURE ONE”, “ESACURE KIP150”, “ESACURE KIP160”, “ESACURE 1001M”, “ESACURE A198”, “ESACURE KIP IT”, “ESACURE KTO46”, “ESACURE TZT” (all manufactured by Fratelli-Lamberti SpA”), “SPEEDCURE BMS”, “SPEEDCURE PBZ”, and “benzophenone” (manufactured by LAMBSON Ltd.). In addition, a photoacid generator can be used as a photocationic initiator. Examples of the photoacid generator include a diazodisulfone-based compound, a triphenylsulfonium-based compound, a phenylsulfone-based compound, a sulfonylpyridine-based compound, a triazine-based compound, and a diphenyliodonium compound.
The content of the photopolymerization initiator is preferably 0.1% to 10% and particularly preferably 1% to 6% by mass with respect to the total content of the polymerizable compound contained in the polymerizable composition. These may be used alone or in combination of two or more kinds thereof.
Further, as a thermal polymerization initiator used for thermal polymerization, conventionally known initiators can be used, and examples thereof include an organic peroxide such as methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bins(4-t-butylcyclohexyl)peroxy dicarbonate, t-butylperoxy benzoate, methyl ethyl ketone peroxide, 1,1-bis(t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydroperoxide, dicumyl peroxide, isobutyl peroxide, di(3-methyl-3-methoxybutyl)peroxy dicarbonate, or 1,1-bis(t-butylperoxy)cyclohexane; an azonitrile compound such as 2,2′-azobisisobutyronitrile or 2,2′-azobis(2,4-dimethylvaleronitrile); an azoamidine compound such as 2,2′-azobis(2-methyl-N-phenylpropion-amidine)dihydrochloride; an azoamide compound such as 2,2′ azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]p ropionamide}; and an alkylazo compound such as 2,2′ azobis(2,4,4-trimethylpentane). The content of the thermal polymerization initiator is preferably 0.1% to 10% and particularly preferably 1% to 6% by mass. These may be used alone or in combination of two or more kinds thereof.
The polymerizable composition of the present invention may contain an organic solvent as necessary. The organic solvent to be used is not particularly limited, but an organic solvent that satisfactorily dissolves the polymerizable compound is preferable and an organic solvent which can be dried at a temperature of 100° C. or lower is preferable. Examples of such solvents include aromatic hydrocarbon such as toluene, xylene, cumene, or mesitylene, an ester-based solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, 3-butoxymethyl acetate, or ethyl lactate, a ketone-based solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or cyclopentanone, an ether-based solvent such as tetrahydrofuran, 1,2-dimethoxyethane, or anisole, an amide-based solvent such as N,N-dimethylformamide or N-methyl-2-pyrrolidone, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol monomethyl propyl ether, diethylene glycol monomethyl ether acetate, γ-butyrolactone, and chlorobenzene. These may be used alone or in combination of two or more kinds thereof. From the viewpoint of solution stability, it is preferable to use one or more solvents selected from a ketone-based solvent, an ether-based solvent, an ester-based solvent, and an aromatic hydrocarbon-based solvent.
Since the polymerizable composition used in the present invention is typically used by application, the proportion of the organic solvent to be used is not particularly limited as long as the applied state is not significantly impaired, but the content of the organic solvent is preferably used such that the ratio of the total content of the polymerizable compound contained in the polymerizable composition is 0.1% to 99% by mass, more preferably 5% to 60% by mass, and particularly preferably 10% to 50% by mass.
Further, it is preferable that the polymerizable liquid crystalline compound is dissolved in the organic solvent by heating and stirring the solution in order for the compound to be uniformly dissolved therein. The heating temperature during the heating and the stirring may be adjusted as appropriate by considering the dissolution of the polymerizable liquid crystal composition in the organic solvent, but is preferably 15° C. to 130° C., more preferably 30° C. to 110° C., and particularly preferably 50° C. to 100° C. from the viewpoint of productivity.
The polymerizable composition of the present invention may include general-purpose additives depending on various purposes thereof. For example, additives such as a polymerization inhibitor, an antioxidant, an ultraviolet absorbing agent, an alignment controlling agent, a chain transfer agent, an infrared absorbing agent, a thixotropic agent, an antistatic agent, a dye, a filler, a chiral compound, a non-liquid crystalline compound having a polymerizable group, a liquid crystal compound, and an alignment material can be added to the extent that does not significantly degrade alignment properties of liquid crystals.
The polymerizable composition of the present invention may contain a polymerization inhibitor as necessary. The polymerization inhibitor to be used is not particularly limited, and conventionally known polymerization inhibitors can be used.
Examples thereof include a phenol-based compound such as p-methoxyphenol, cresol, t-butyl catechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2′-methylenebis(4-methyl-6-t-butylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, or 4,4′-dialkoxy-2,2′-bi-1-naphthol; a quinone-based compound such as hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinione, or diphenoquinione; an amine-based compound such as p-phenylenediamine, 4-amninodiphenylamine, N,N′-diphenyl-p-phenylenediamine, N-i-propyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N,N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthyamine, 4,4′-dicumyl-diphenylamine, or 4,4′-dioctyl-diphenylamine; a thioether-based compound such as phenothiazine or distearyl thiodipropionate; and a nitroso compound such as N-nitrosodipheylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxyamine ammonium salt, nitrosobenzene, 2,4,6-tri-tert-butylnitrobenizene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, or 2-nitroso-5-methylaminophenol hydrochloride.
The amount of the polymerization inhibitor to be added is preferably 0.01% to 1.0% by mass and more preferably 0.05% to 0.5% by mass with respect to the total amount of the polymerizable compound contained in the polymerizable composition.
The polymerizable composition of the present invention may contain an antioxidant as necessary. Examples of such a compound include a hydroquinone derivative, a nitrosoamine-based polymerization inhibitor, and a hindered phenol-based antioxidant, and more specific examples thereof include tert-butylhydroquinone, “Q-1300” and “Q-1301” (both manufactured by Wako Pure Chemical Industries, Ltd.), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate “IRGANOX 1010”, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate “IRGANOX 1035”, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate “IRGANOX 1076”, “IRGANOX 1135”, “IRGANOX 1330”, 4,6-bis(octylthiomethyl)-o-cresol “IRGANOX 1520L”, “IRGANOX 1726”, “IRGANOX 245”, “IRGANOX 259”, “IRGANOX 3114”, “IRGANOX 3790”, “IRGANOX 5057”, “IRGANOX 565” (all manufactured by BASF SE), ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 (all manufactured by ADEKA CORPORATION), SUMILIZER BHT, SUMILIZER BBM-S, and SUMILIZER GA-80 (manufactured by Sumitomo Chemical Industries Co., Ltd.).
The amount of the antioxidant to be added is preferably 0.01% to 2.0% by mass and more preferably 0.05% to 1.0% by mass with respect to the total amount of the polymerizable compound contained in the polymerizable composition.
The polymerizable composition of the present invention may contain an ultraviolet absorbing agent and a light stabilizer as necessary. The ultraviolet absorbing agent or the light stabilizer to be used is not particularly limited, but it is preferable to use an optically anisotropic body or an optical film in order to improve light resistance.
Examples of the ultraviolet absorbing agent include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole “TINUVIN PS”, “TINUVIN 99-2”, “TINUVIN 109”, “TINUVIN 213”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 328”, “TINUVIN 329”, “TINUVIN 384-2”, “TINUVIN 571”, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol “TINUVIN 900”, 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol “TINUVIN 928”, “TINUVIN 1130”, “TINUVIN 400”, “TINUVIN 405”, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine “TINUVIN 460”, “TINUVIN 479”, “TINUVIN 5236” (all manufactured by BASF SE), “ADEKA STAB LA-32”, “ADEKA STAB LA-34”, “ADEKA STAB LA-36”, “ADEKA STAB LA-31”, “ADEKA STAB LA-1413”, and “ADEKA STAB LA-51” (all manufactured by ADEKA CORPORATION).
Examples of the light stabilizer include “TINUVIN 111FDL”, “TINUVIN 123”, “TINUVIN 144”, “TINUVIN 152”, “TINUVIN 292”, “TINUVIN 622”, “TINUVIN 770”, “TINUVIN 765”, “TINUVIN 780”, “TINUVIN 905”, “TINUVIN 5100”, “TINUVIN 5050”, “TINUVIN 5060”, “TINUVIN 5151”, “CHIMASSORB 119FL”, “CHIMASSORB 944FL”, “CHIMASSORB 944LD” (all manufactured by BASF SE), “ADEKA STAB LA-52”, “ADEKA STAB LA-57”, “ADEKA STAB LA-62”, “ADEKA STAB LA-67”, “ADEKA STAB LA-63P”, “ADEKA STAB LA-68LD”, “ADEKA STAB LA-77”, “ADEKA STAB LA-82”, and “ADEKA STAB LA-87” (all manufactured by ADEKA CORPORATION).
The polymerizable composition of the present invention may contain an alignment controlling agent in order to control the alignment state of the liquid crystalline compound. As the alignment controlling agent to be used, agents used for substantial horizontal alignment, substantial vertical alignment, or substantial hybrid alignment of the liquid crystalline compound with respect to the base material may be exemplified. Further, in the case where a chiral compound is added, agents used for substantial plane alignment of the liquid crystalline compound with respect to the base material may be exemplified. As described above, horizontal alignment or plane alignment may be induced by a surfactant in some cases, the alignment controlling agent is not particularly limited as long as the alignment state of each liquid crystalline compound is induced, and conventionally known ones can be used.
As such an alignment controlling agent, a compound which has an effect of effectively reducing the tilt angle between the interface of the air and an optically anisotropic body in the case where an optically anisotropic body is used as the polymerizable liquid crystal composition, has a repeating unit represented by Formula (8), and has a weight-average molecular weight of 100 to 1,000,000 may be exemplified.
[Chem. 114]
CR11R12—CR13R14 (8)
(In the formula, R11, R12, R13, and R14 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms in the hydrocarbon group may be substituted with one or more halogen atoms.)
In addition, examples of the compound include a rod-like liquid crystalline compound modified with a fluoroalkyl group, a discotic liquid crystalline compound, and a polymerizable compound containing a long-chain aliphatic alkyl group which may have a branched structure.
Examples of the compound which has an effect of effectively increasing the tilt angle between the interface of the air and an optically anisotropic body in the case where an optically anisotropic body is used as the polymerizable liquid crystal composition include cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, a rod-like liquid crystalline compound modified with a heteroaromatic ring salt, a cyano group, and a rod-like liquid crystalline compound modified with a cyanoalkyl group.
The polymerizable composition of the present invention may contain a chain transfer agent in order to further improve adhesiveness among the polymer, the optically anisotropic body, and the base material. Examples of the chain transfer agent include aromatic hydrocarbons, halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane, a mercaptan compound such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl, n-dodecyl mercaptan, t-tetradecyl mercaptan, or t-dodecyl mercaptan, a thiol compound such as hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, or 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, a sulfide compound such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, or tetrabutyl thiuram disulfide, N,N-dimethylaniline, N,N-divinylaniline, pentaphenylethane, an α-methylstyrene dimer, acrolein, allyl alcohol, terpineol, α-terpinene, γ-terpinene, and dipentene. Among these, 2,4-diphenyl-4-methyl-1-pentene and a thiol compound are more preferable.
Specifically, compounds represented by General Formulae (9-1) to (9-12) are preferable.
In the formulae, R95 represents an alkyl group having 2 to 18 carbon atoms, the alkyl group may be linear or branched, one or more methylene groups in the alkyl group may be substituted with an oxygen atom, a sulfur atom, —CO—, —OCO—, —COO—, or —CH═CH— by assuming that an oxygen atom and a sulfur atom are not directly bonded to each other, R96 represents an alkylene group having 2 to 18 carbon atoms, and one or more methylene groups in the alkylene group may be substituted with an oxygen atom, a sulfur atom, —CO—, —OCO—, —COO—, or —CH═CH— by assuming that an oxygen atom and a sulfur atom are not directly bonded to each other.
It is preferable that the chain transfer agent is added during a step of preparing a polymerizable solution by mixing the polymerizable liquid crystal compound in an organic solvent and heating and stirring the solution, but the chain transfer agent may be added during the subsequent step of mixing a polymerization initiator into the polymerizable solution or may be added during both steps.
The amount of the chain transfer agent to be added is preferably 0.5% to 10% by mass and more preferably 1.0% to 5.0% by mass with respect to the total amount of the polymerizable compound contained in the polymerizable composition.
Further, a liquid crystal compound or the like which is not polymerizable can be added as necessary for the purpose of adjusting physical properties. It is preferable that the polymerizable compound which does not have liquid crystallinity is added during a step of preparing a polymerizable solution by mixing the polymerizable compound in an organic solvent and heating and stirring the solution, but the liquid crystal compound which is not polymerizable may be added during the subsequent step of mixing a polymerization initiator into the polymerizable solution or may be added during both steps. The amount of these compounds to be added is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less with respect to the polymerizable composition.
The polymerizable composition of the present invention may contain an infrared absorbing agent as necessary. The infrared absorbing agent to be used is not particularly limited and the polymerizable liquid crystal composition may contain conventionally known ones within the range that does not impair the alignment properties.
Examples of the infrared absorbing agent include a cyanine compound, a phthalocyanine compound, a naphthoquinone compound, a dithiol compound, a diimmonium compound, an azo compound, and an ammonium salt.
Specific examples thereof include diimmonium salt type “NIR-IM1”, ammonium salt type “NIR-AM1” (both manufactured by Nagase ChemteX Corporation), “KARENZ IR-T”, “KARENZ IR-13F” (both manufactured by SHOWA DENKO K.K.), “YKR-2200”, “YKR-2100” (both manufactured by Yamamoto Chemicals Inc.), “IRA908”, “IRA931”, “IRA955”, and “IRA1034” (all manufactured by INDECO Co., Ltd.).
The polymerizable composition of the present invention may contain an antistatic agent as necessary. The antistatic agent to be used is not particularly limited and the polymerizable liquid crystal composition may contain conventionally known ones within the range that does not impair the alignment properties.
Examples of such an antistatic agent include a polymer compound containing at least one or more sulfonate groups or phosphate groups in a molecule, a compound containing a quaternary ammonium salt, and a surfactant containing a polymerizable group.
Among these, a surfactant containing a polymerizable group is preferable, and examples of an anionic surfactant containing a polymerizable group include alkyl ether-based surfactants such as “ANTOX SAD”, “ANTOX MS-2N” (both manufactured by Nippon Nyukazai Co., Ltd.), “AQUALON KH-05”, “AQUALON KH-10”, “AQUALON KH-20”, “AQUALON KH-0530”, “AQUALON KH-1025” (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), “ADEKA REASOAP SR-10N”, “ADEKA REASOAP SR-20N” (both manufactured by ADEKA CORPORATION), and “LATEMUL PD-104” (manufactured by Kao Corporation), sulfosuccinic acid ester-based surfactants such as “LATEMUL S-120”, “LATEMUL S-120A”, “LATEMUL S-180P”, “LATEMUL S-180A” (manufactured by Kao Corporation), and “ELEMINOL JS-2” (manufactured by Sanyo Chemical Industries, Ltd.), alkylphenylether-based or alkylphenylester-based surfactants such as “AQUALON H-2855A”, “AQUALON H-3855B”, “AQUALON H-3855C”, “AQUALON H-3856”, “AQUALON HS-05”, “AQUALON HS-10”, “AQUALON HS-20”, “AQUALON HS-30”, “AQUALON HS-1025”, “AQUALON BC-05”, “AQUALON BC-10”, “AQUALON BC-20”, “AQUALON BC-1025”, and “AQUALON BC-2020” (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), “ADEKA REASOAP SDX-222”, “ADEKA REASOAP SDX-223”, “ADEKA REASOAP SDX-232”, “ADEKA REASOAP SDX-233”, “ADEKA REASOAP SDX-259”, “ADEKA REASOAP SE-10N”, and “ADEKA REASOAP SE-20N” (all manufactured by ADEKA CORPORATION), (meth)acrylate sulfuric acid ester-based surfactants such as “ANTOX MS-60”, “ANTOX MS-2N” (both manufactured by Nippon Nyukazai Co., Ltd.), “ELEMINOL RS-30” (manufactured by Sanyo Chemical Industries, Ltd.), and phosphoric acid ester-based surfactants such as “H-3330P” (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and “ADEKA REASOAP PP-70” (manufactured by ADEKA CORPORATION).
Among the surfactants containing a polymerizable group, examples of a non-ionic surfactant include alkyl ether-based surfactants such as “ANTOX LMA-20”, “ANTOX LMA-27”, “ANTOX EMH-20”, “ANTOX LMH-20”, “ANTOX SMH-20” (all manufactured by Nippon Nyukazai Co., Ltd.), “ADEKA REASOAP ER-10”, “ADEKA REASOAP ER-20”, “ADEKA REASOAP ER-30”, “ADEKA REASOAP ER-40” (all manufactured by ADEKA CORPORATION), “LATEMUL PD-420”, “LATEMUL PD-430”, and “LATEMUL PD-450” (all manufactured by Kao Corporation), alkyl phenyl ether-based or alkyl phenyl ester-based surfactants such as “AQUALON RN-10”, “AQUALON RN-20”, “AQUALON RN-30”, “AQUALON RN-50”, “AQUALON RN-2025” (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), “ADEKA REASOAP NE-10”, “ADEKA REASOAP NE-20”, “ADEKA REASOAP NE-30”, and “ADEKA REASOAP NE-40” (all manufactured by ADEKA CORPORATION), and (meth)acrylate sulfuric acid ester-based surfactants such as “RMA-564”, “RMA-568”, and “RMA-1114” (all manufactured by Nippon Nyukazai Co., Ltd.).
Other examples of antistatic agents include polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, propoxy polyethylene glycol (meth)acrylate, n-butoxy polyethylene glycol (meth)acrylate, n-pentaxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, ethoxy polypropylene glycol (meth)acrylate, propoxy polypropylene glycol (meth)acrylate, n-butoxy polypropylene glycol (meth)acrylate, n-pentaxy polypropylene glycol (meth)acrylate, phenoxy polypropylene glycol (meth)acrylate, polytetramethylene glycol (meth)acrylate, methoxy polytetramethylene glycol (meth)acrylate, phenoxy tetraethylene glycol (meth)acrylate, hexaethylene glycol (meth)acrylate, and methoxy hexaethylene glycol (meth)acrylate.
The antistatic agent can be used alone or in combination of two or more kinds thereof. The amount of the antistatic agent to be added is preferably 0.001% to 10% by weight and more preferably 0.01% to 5% by weight with respect to the total amount of the polymerizable compound contained in the polymerizable composition.
The polymerizable composition of the present invention may contain a dye as necessary. The dye to be used is not particularly limited and the polymerizable liquid crystal composition may contain conventionally known ones within the range that does not impair the alignment properties.
Examples of the dye include dichroic dyes and fluorescent dyes. Examples of such dyes include a polyazo dye, an anthraquinone dye, a cyanine dye, a phthalocyanine dye, a perylene dye, and a perinone dye, and a squarylium dye. From the viewpoint of addition, a dye exhibiting liquid crystallinity is preferable as the dye.
For example, dyes described in U.S. Pat. No. 2,400,877, Dreyer J. F., Phys. and Colloid Chem., 1948, 52, 808., “The Fixing of Molecular Orientation”, Dreyer J. F., Journal de Physique, 1969, 4, 114., “Light Polarization from Films of Lyotropic Nematic Liquid Crystals”, J. Lydon, “Chromonics” in “Handbook of Liquid Crystals Vol. 2B: Low Molecular Weight Liquid Crystals II”, D. Demus, J. Goodby, G. W. Gray, H. W. Spiessm, V. Vill ed, Willey-VCH, pp. 981-1007 (1998), Dichroic Dyes for Liquid Crystal Display A. V. ivashchenko CRC Press, 1994, and “New Development of Functional Dye Market”, Chapter 1, pp. 1, 1994, published by CMC Corporation can be used.
Examples of the dichroic dyes include dyes represented by Formulae (d-1) to (d-8). The amount of the dichroic dye to be added is preferably 0.001% to 10% by weight and more preferably 0.01% to 5% by weight with respect to the total amount of the polymerizable compound contained in the polymerizable composition.
(Filler) The polymerizable composition of the present invention may contain a filler as necessary. The filler to be used is not particularly limited, and the polymerizable liquid crystal composition may contain conventionally known ones within the range that does not degrade the thermal conductivity of the obtained polymer.
Examples of the filler include inorganic fillers such as alumina, titanium white, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide, and glass fibers, thermally conductive fillers such as metal powder, for example, silver powder or copper powder, aluminum nitride, boron nitride, silicon nitride, gallium nitride, silicon carbide, magnesia (aluminum oxide), alumina (aluminum oxide), crystalline silica (silicon oxide), fused silica (silicon oxide), and silver nanoparticles.
The polymerizable composition of the present invention may contain a chiral compound for the purpose of obtaining a chiral nematic phase. The chiral compound itself does not need to exhibit liquid crystallinity and may or may not contain a polymerizable group. Further, the orientation of the spiral of the chiral compound can be appropriately selected depending on the applications of the polymer.
The chiral compound containing a polymerizable group is not particularly limited, and conventionally known compounds can be used. Among those, a chiral compound with large helical twisting power (HTP) is preferable. Further, as the polymerizable group, a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, an acryloyloxy group, a methacryloyloxy group, a glycidyl group, and an oxetanyl group are preferable and an acryloyloxy group, a glycidyl group, and an oxetanyl group are particularly preferable.
It is necessary that the amount of the chiral compound to be blended is adjusted as appropriate by the spiral inductive force of the compound, and the amount thereof is preferably 0.5% to 80% by mass, more preferably 3% to 50% by mass, and particularly preferably 5% to 30% by mass with respect to the total amount of the liquid crystalline compound containing a polymerizable group and the chiral compound containing a polymerizable group.
Specific examples of the chiral compound include compounds represented by General Formulae (10-1) to (10-4), but the examples are not limited to the compounds represented by the following general formulae.
In the formulae, Sp5a and Sp5b each independently represent an alkylene group having 0 to 18 carbon atoms, the alkylene group may be substituted with one or more halogen atoms, a CN group, or an alkyl group having a polymerizable functional group and 1 to 8 carbon atoms, and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in this group may be each independently substituted with —O—, —S—, —NH—, —N(CH3)—, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, or —C≡C— in the form in which oxygen atoms are not directly bonded to each other.
A1, A2, A3, A4, A5, and A6 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 thiophene-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, a 1,4-naphthylene group, a benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl group, a benzo[1,2-b:4,5-b′]diselenophene-2,6-diyl group, a [1]benzothieno[3,2-b]thiophene-2,7-diyl group, a [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or a fluorene-2,7-diyl group, n, l, and k each independently represent 0 or 1, n+l+k is greater than or equal to 0 and less than or equal to 3,
m5 represents 0 or 1,
Z0, z1, Z2, Z3, Z4, Z5, and Z6 each independently represent —COO—, —OCO—, —CH2CH2—, —OCH2—, —CH2O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH2CH2COO—, —CH2CH2OCO—, —COOCH2CH2—, —OCOCH2CH2—, —CONH—, —NHCO—, an alkyl group which may have halogen atoms with 2 to 10 carbon atoms, or a single bond,
R5a and R5b each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, the alkyl group may be substituted with one or more halogen atoms or CN, one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in this group may be each independently substituted with —O—, —S—, —NH—, —N(CH3)—, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, or —C≡C— in the form in which oxygen atoms are not directly bonded to each other. Alternatively, R5a and R5b represent a group represented by Formula (10-a).
[Chem. 120]
—P5a (10-a)
(In the formula, P5a represents a polymerizable functional group and Sp5a has the same definition as that for Sp1.)
P5a represents a substituent selected from polymerizable groups represented by Formulae (P-1) to (P-20).
Other specific examples of the chiral compound include compounds represented by General Formulae (10-5) to (10-35).
In the formulae, m and n each independently represent an integer of 1 to 10, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, and in the case where a plurality of R is present, these may be the same as or different from each other.
Specific examples of the chiral compound which does not contain a polymerizable group include cholesterol pelargonate and cholesterol stearate which contain a cholesteryl group as a chiral group; “CB-15”, “C-15” (manufactured by BDH Corporation), “S-1082” (manufactured by Merch Japan), “CM-19”, “CM-20”, and “CM” (manufactured by CHISSO CORPORATION) which contain a 2-methylbutyl group as a chiral group; and “S-811” (manufactured by Merch Japan), “CM-21”, and “CM-22” (manufactured by CHISSO CORPORATION) which contain a 1-methylheptyl group as a chiral group.
In the case where the chiral compound is added, the amount of the chiral compound to be added may vary depending on the applications of the polymer of the polymerizable liquid crystal composition of the present invention, but the amount thereof is determined such that a value (d/P) obtained by dividing a thickness (d) of the polymer to be obtained by a spiral pitch (P) in the polymer is to be preferably 0.1 to 100 and more preferably 0.1 to 20.
A compound which is not a liquid crystal compound containing a polymerizable group can be added to the polymerizable composition of the present invention. Such a compound can be used without particular limitation as long as the compound is usually recognized as a polymerizable monomer or a polymerizable oligomer in the technical field. In the case where the compound is added, the content thereof is preferably 15% by mass or less and more preferably 10% by mass or less with respect to the total amount of the polymerizable compound contained in the polymerizable composition.
Specific examples of the compound include mono(meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxy ethyl acrylate, propyl (meth)acrylate, 2-hydroxy propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 4-hydroxy butyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, octyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyloxyl ethyl (meth)acrylate, isobornyloxyl ethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyl adamantly (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, methoxy ethyl (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxy ethyl (meth)acrylate, 2-phenoxy diethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxy ethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth)acrylate, (3-ethyloxetan-3-yl) methyl (meth)acrylate, o-phenyl phenol ethoxy (meth)acrylate, dimethylamino (meth)acrylate, diethylamino (meth)acrylate, 2,2,3,3,3,-pentafluoropropyl (meth)acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate, 2-(perfluorobutyl) ethyl (meth)acrylate, 2-(perfluorohexyl) ethyl (meth)acrylate, 1H,1H,3H-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate, 1H-1-(trifluoromethyl) trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl (meth)acrylate, 1H, 1H-pentadecafluorooctyl (meth)acrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, 2-(meth)acryloyloxy ethyl phthalic acid, 2-(meth)acryloyloxy ethyl hexahydrophthalic acid, glycidyl (meth)acrylate, 2-(meth)acryloyloxy ethyl phosphoric acid, acryloyl morpholine, dimethyl acrylamide, dimethylamino propyl acrylamide, isopropyl acrylamide, diethyl acrylamide, hydroxy ethyl acrylamide, or N-acryloyloxy ethyl hexahydrophthalimide; diacrylate such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyldiol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, an acrylic acid adduct of 1,6-hexanediol diglycidyl ether, or an acrylic acid adduct of 1,4-butanediol diglycidyl ether; tri(meth)acrylate such as trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri(meth)acrylate, or ϵ-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate; tetra(meth)acrylate such as pentaerythritol tetra(meth)acrylate or ditrimethylolpropane tetra(meth)acrylate; an ethoxy compound such as dipentaerythritol hexa(meth)acrylate, oligomer type (meth)acrylate, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, or bisphenol A diglycidyl ether; and maleimide. These may be used alone or in combination of two or more kinds thereof.
(Other Liquid Crystalline Compounds)
The polymerizable composition used in the present invention may contain a liquid crystalline compound having one or more polymerizable groups in addition to the liquid crystalline compounds of General Formulae (1) to (7). However, if the add amount is too much, the phase difference ratio of a retardation plate obtained using the polymerizable composition may increase, and thus the add amount is preferably 30 mass % or less with respect to the total amount of the polymerizable compounds in the polymerizable composition of the present invention, more preferably 10 mass % or less, and particularly preferably 5 mass % or less.
Examples of such liquid crystalline compounds include liquid crystalline compounds of General Formula (1-b) to General Formula (7-b).
(In the formula, P11 to P74 represent a polymerizable group, S11 to S72 represent a spacer group or a single bond, and in the case where plural groups are present with respect to each of S11 to S72, these may be the same as or different from each other;
X11 to X72 represent —O—, —S—, —OCH2—, —CH2O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where a plurality of X11's to X72's are present, these may be the same as or different from each other, provided that each of P—(S—X)— bonds does not have —O—O—;
MG11 to MG71 each independently represent formula (b):
[Chem. 130]
A83-Z83j83M81Z84-A84j84 (b)
(In the formula, A83 and A84 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group, these groups may be unsubstituted or substituted with one or more L2's, and in the case where plural groups are present with respect to each of A83 and A84, these may be the same as or different from each other;
Z83 and Z84 each independently represent —O—, —S—, —OCH2—, —CH2O—, —CH2CH2—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CH═CH—, —N═N—, —CH═N—, —N═CH—, —CH═N—N═CH—, —CF═CF—, —C≡C—, or a single bond, and in the case where plural groups are present with respect to each of Z83 and Z84, these may be the same as or different from each other;
M81 represents a group selected from 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 thiophene-2,5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a naphthylene-1,4-diyl group, a naphthylene-1,5-diyl group, a naphthylene-1,6-diyl group, a naphthylene-2,6-diyl 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, a benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl group, a benzo[1,2-b:4,5-b′]diselenophene-2,6-diyl group, a [1]benzothieno[3,2-b]thiophene-2,7-diyl group, a [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, and a fluorene-2,7-diyl group, and these groups may be unsubstituted or substituted with one or more L2's;
L2 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxy group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, and one or more of arbitrary hydrogen atoms may be substituted with a fluorine atom, and in the case where a plurality of L2's are present in the compound, these may be the same as or different from each other; m represents an integer of 0 to 8; j83 and j84 each independently represent an integer of 0 to 5; and j83+j84 represents an integer of 1 to 5.);
R11 and R31 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—; m11 represents an integer of 0 to 8; and m2 to m7, n2 to n7, 14 to 16, and k6 each independently represent an integer of 0 to 5, provided that compounds represented by General Formula (1) to General Formula (7) are excluded).
Preferred specific examples of the compound represented by General Formula (1-b) include compounds represented by Formula (1-b-1) to Formula (1-b-39).
(In the formulae, m11 and n11 each independently represent an integer of 1 to 10, R111 and R112 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, R113 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms in which one —CH2— or two or more (—CH2—)'s which are not adjacent to each other may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, and one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (2-b) include compounds represented by Formula (2-b-1) to Formula (2-b-33).
(In the formulae, m and n each independently represent an integer of 1 to 18, and R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. In the case where these groups represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all groups may be unsubstituted or substituted with one or two or more halogen atoms.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (3-b) include compounds represented by Formula (3-b-1) to Formula (3-b-16).
These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (4-b) include compounds represented by Formula (4-b-1) to Formula (4-b-29).
(In the formulae, m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. In the case where these groups represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all groups may be unsubstituted or substituted with one or two or more halogen atoms.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (5-b) include compounds represented by Formula (5-b-1) to Formula (5-b-26).
(In the formulae, n each independently represents an integer of 1 to 10, and R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. In the case where these groups represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all groups may be unsubstituted or substituted with one or two or more halogen atoms.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (6-b) include compounds represented by Formula (6-b-1) to Formula (6-b-23).
(In the formulae, k, 1, m, and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. In the case where these groups represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all groups may be unsubstituted or substituted with one or two or more halogen atoms.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
Preferred specific examples of the compound represented by General Formula (7-b) include compounds represented by Formula (7-b-1) to Formula (7-b-25).
(In the formulae, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. In the case where these groups represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all groups may be unsubstituted or substituted with one or two or more halogen atoms.) These liquid crystalline compounds may be used singly or two or more thereof may be mixed to be used.
The polymerizable composition of the present invention may contain an alignment material that improves alignment properties in order to improve alignment properties. Conventionally known one can be used as the alignment material as long as the material is soluble in a solvent that dissolves the liquid crystalline compound containing a polymerizable group, which is used for the polymerizable composition of the present invention, and the alignment material can be added within the range that does not significantly degrade the alignment properties through addition. Specifically, the amount of the alignment material is preferably 0.05% to 30% by weight, more preferably 0.5% to 15% by weight, and particularly preferably 1% to 10% by weight with respect to the total amount of the polymerizable compound contained in the polymerizable composition.
Specific examples of the alignment material include photoisomerizing or photodimerizing compounds such as polyimide, polyamide, a benzocyclobutene (BCB) polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, an epoxy resin, an epoxy acrylate resin, an acrylic resin, a coumarin compound, a chalcone compound, a cinnamate compound, a fulgide compound, an anthraquinone compound, an azo compound, and an aryl ethene compound. Further, materials (photo-alignment materials) that are aligned by irradiation with ultraviolet rays or irradiation with visible light are preferable.
Examples of the photo-alignment materials include polyimide having cyclic cycloalkane, wholly aromatic polyarylate, polyvinyl cinnamate described in JP-A-5-232473, polyvinyl ester of paramethoxycinnamic acid, a cinnamate derivative described in JP-A-06-287453 and JP-A-06-289374, and a maleimide derivative described in JP-A-2002-265541. Specifically, compounds represented by Formulae (12-1) to (12-7) are preferable.
In the formulae, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, or a nitro group, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, the alkyl group may be linear or branched, one or more of arbitrary hydrogen atoms in the alkyl group may be substituted with a fluorine atom, one —CH2— or two or more (—CH2—)'s which are not adjacent to each other in the alkyl group may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, and CH3 at the terminal may be substituted with CF3, CCl3, a cyano group, a nitro group, an isocyano group, a thioisocyano group. n represents an integer of 4 to 100,000 and m represents an integer of 1 to 10.
The polymerizable composition of the present invention preferably has low wavelength dispersion or reverse wavelength dispersion. Above all, the value of:
Re(450 nm)/Re(550 nm)
(wherein Re(450 nm) represents an in-plane phase difference at a wavelength of 450 nm when the polymerizable composition is aligned on a substrate in a horizontal direction to the substrate, and Re(550 nm) represents an in-plane phase difference at a wavelength of 550 nm when the polymerizable composition is aligned on a substrate in a horizontal direction to the substrate) of the composition is preferably 0.70 to 0.95, more preferably 0.80 to 0.90.
The polymer of the present invention is obtained by performing polymerization in a state in which the polymerizable composition of the present invention contains an initiator. The polymer of the present invention is used for an optically anisotropic body, a retardation film, a lens, a colorant, a printed matter, and the like.
The optically anisotropic body of the present invention is obtained by coating a base material or a base material having an alignment function with the polymerizable composition of the present invention, uniformly aligning liquid crystal molecules in the polymerizable liquid crystal composition of the present invention in a state in which a nematic phase or a smectic phase is maintained, and then performing polymerization.
A base material used for the optically anisotropic body of the present invention is a material that is typically used for a liquid crystal display element, an organic light-emitting display element, other display elements, an optical component, a colorant, a marking, printed matter, or an optical film and is not particularly limited as long as the material has heat resistance so that the material can withstand heating during the drying after the application of the polymerizable composition solution of the present invention. Examples of such a material include organic materials such as a glass base material, a metal base material, a ceramic base material, a plastic base material, and paper. Particularly in the case where the base material is an organic material, examples of the organic material include a cellulose derivative, polyolefin, polyester, polyolefin, polycarbonate, polyacrylate, polyarylate, polyether sulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene. Among these, plastic base materials such as polyester, polystyrene, polyolefin, a cellulose derivative, polyarylate, and polycarbonate are preferable. As the shape of the base material, a base material having a curved surface may be used in addition to a flat plate. These base materials may have an electrode layer, an anti-reflection function, or a reflection function as necessary.
In order to improve the coating properties of the polymerizable composition of the present invention or the adhesiveness between the base material and the polymer, the base material may be subjected to a surface treatment. Examples of the surface treatment include an ozone treatment, a plasma treatment, a corona treatment, and a silane coupling treatment. Further, in order to adjust the transmittance or reflectance of light, an organic thin film, an inorganic oxide thin film, or a metal thin film may be provided on the surface of the base material according to a vapor deposition method. Alternatively, the base material may be a pickup lens, a rod lens, an optical disc, a retardation film, a light diffusion film, or a color filter in order to add the optical added value. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that increase the added value are preferable.
Further, the base material may be subjected to a typical alignment treatment or provided with an alignment film so that the polymerizable composition is aligned when a polymerizable composition solution of the present invention is applied and dried. Examples of the alignment treatment include a stretching treatment, a rubbing treatment, a polarized ultraviolet visible light irradiation treatment, an ion beam treatment, and an oblique vapor deposition treatment of SiO2 performed on a base material. In the case of using an alignment film, conventionally known alignment films are used. Examples of such alignment films include compounds such as polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, an epoxy resin, an epoxy acrylate resin, an acrylic resin, an azo compound, a coumarin compound, a chalcone compound, a cinnamate compound, a fulgide compound, an anthraquinone compound, an azo compound, and an aryl ethene compound and polymers or copolymers of these compounds. As a compound that is subjected to an alignment treatment through rubbing, a compound that promotes crystallization of a material by performing a heating process during or after the alignment treatment is preferable. Among the compounds that are subjected to alignment treatments other than the rubbing treatment, compounds for which photo-alignment materials are used are preferable.
In the case where the liquid crystal composition is brought into contact with a substrate having an alignment function, liquid crystal molecules are aligned along a direction in which the substrate has been subjected to the alignment treatment in the vicinity of the substrate. The method of the alignment treatment performed on the substrate greatly affects whether the liquid crystal molecules are aligned horizontally to the substrate or aligned obliquely or vertically to the substrate. For example, a polymerizable liquid crystal layer that is aligned substantially horizontal is obtained when an alignment film having an extremely small pretilt angle, such as a film used for an in-plane switching (IPS) type liquid crystal display element, is provided on the substrate.
Further, in the case where an alignment film, such as a film used for a TN type liquid crystal display element, is provided on the substrate, a polymerizable liquid crystal layer that is slightly obliquely aligned is obtained. In the case where an alignment film, such as a film used for an STN type liquid crystal display element, is used, a polymerizable liquid crystal layer that is largely obliquely aligned is obtained.
As a coating method used to obtain the optically anisotropic body of the present invention, conventionally known methods such as an applicator method, a bar coating method, a spin coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, a flexo coating method, an inkjet method, a die coating method, a cap coating method, a dip coating method, a slit coating method, and a spray coating method can be used. The polymerizable composition is dried after the coating.
After the coating, it is preferable that the liquid crystal molecules of the polymerizable composition of the present invention are uniformly aligned in a state in which a smectic phase or a nematic phase is maintained. As an example for this, a heat treatment method may be exemplified. Specifically, the substrate is coated with the polymerizable composition of the present invention, the polymerizable composition is heated at an N (nematic phase)-I (isotropic liquid phase) transition temperature (hereinafter, abbreviated as the N-I transition temperature) of the liquid crystal composition or higher so that the liquid crystal composition enters an isotropic phase liquid state. Thereafter, the resultant is gradually cooled to exhibit a nematic phase. At this time, it is desirable that a liquid crystal phase domain is allowed to be sufficiently grown to obtain a monodomain by temporarily maintaining the temperature at which a liquid crystal phase appears. Alternatively, after the substrate is coated with the polymerizable composition of the present invention, the polymerizable composition may be subjected to a heat treatment of maintaining the temperature range, in which a nematic phase of the polymerizable composition of the present invention appears, for a certain period of time.
When the heating temperature is extremely high, there is a concern that the polymerizable liquid crystal compound may undergo an undesirable polymerizable reaction and deteriorate. Further, when the polymerizable composition is extremely cooled, phase separation occurs in the polymerizable composition, crystals are precipitated, and a high-order liquid crystal phase such as a smectic phase appears. Therefore, the alignment treatment may not be performed.
A homogeneous optically anisotropic body with few alignment defects can be prepared by performing such a heat treatment, compared to a coating method of only performing coating.
After the homogeneous alignment treatment is performed as described above, when the liquid crystal phase is cooled at the lowest temperature at which phase separation does not occur, in other words, the liquid crystal phase is cooled to enter a supercooled state, and polymerization is carried out in a state in which the liquid crystal phase is aligned at the temperature, an optically anisotropic body having a higher alignment order and excellent transparency can be obtained.
The polymerization treatment may be performed on the dried polymerizable composition typically by irradiation with light such as visible ultraviolet rays or by heating in a uniformly aligned state. In the case where the polymerization is performed by irradiation with light, it is preferable that visible ultraviolet light having a wavelength of 420 nm or less is applied and most preferable that ultraviolet light having a wavelength of 250 to 370 nm is applied. Here, in the case where decomposition or the like of the polymerizable composition is caused by visible ultraviolet light having a wavelength of 420 nm or less, it is preferable that a polymerization treatment is performed using visible ultraviolet light having a wavelength of 420 nm or greater in some cases.
As a method of polymerizing the polymerizable composition of the present invention, a method of applying active energy rays or a thermal polymerization method is exemplified. From the viewpoint that heating is not necessary and the reaction proceeds at room temperature, a method of applying active energy rays is preferable. Among the examples thereof, from the viewpoint of a simple operation, a method of applying light such as ultraviolet rays or the like is preferable. The application temperature is set to a temperature at which the liquid crystal phase of the polymerizable composition of the present invention can be maintained, and it is preferable that the temperature thereof is set to 30° C. or lower as much as possible in order to avoid induction of thermal polymerization of the polymerizable composition. Further, the polymerizable liquid crystal composition typically exhibits the liquid crystal phase in the process of raising the temperature, within the N-I transition temperature range from a C (solid phase)-N(nematic) transition temperature (hereinafter, abbreviated as the C-N transition temperature). Further, the polymerizable liquid crystal composition occasionally maintains the liquid crystal state thereof without being solidified at the C-N transition temperature or lower in the process of lowering the temperature, in order to obtain a thermodynamically non-equilibrium state. This state is referred to as a supercooled state. In the present invention, it can be said that the liquid crystal composition in the supercooled state is also in the state of maintaining the liquid crystal phase. Specifically, it is preferable to irradiate with ultraviolet light having a wavelength of 390 nm or less and most preferable to irradiate with light having a wavelength of 250 to 370 nm. In the case where decomposition or the like of the polymerizable composition is caused by the irradiation with ultraviolet light having a wavelength of 390 nm or less, it is preferable that the polymerization treatment is performed using ultraviolet light having a wavelength of 390 nm or greater in some cases. As this light, it is preferable to use diffusion light and non-polarized light. The intensity of irradiation with ultraviolet rays is preferably 0.05 mW/cm2 to 10 W/cm2 and particularly preferably 0.2 mW/cm2 to 2 W/cm2. In the case where the intensity of ultraviolet rays is less than 0.05 mW/cm2, it takes a long time to complete the polymerization. In addition, in the case where the intensity of ultraviolet rays is greater than 2 W/cm2, there is a possibility that the liquid crystal molecules in the polymerizable composition tend to be photodecomposed, a large amount of polymerization heat is generated so that the temperature during the polymerization increases, the order parameter of the polymerizable liquid crystal changes, and the phase difference of the film after the polymerization deviates.
After only a specific portion is polymerized by irradiation with ultraviolet rays using a mask, when the alignment state of the unpolymerized portion is changed by applying an electric field or a magnetic field or raising the temperature and then the unpolymerized portion is polymerized, an optically anisotropic body having a plurality of regions with different alignment directions can be obtained.
Further, an optically anisotropic body having a plurality of regions with different alignment directions can also be obtained by means of restricting the alignment by applying an electric field or a magnetic field to the polymerizable liquid crystal composition or raising a temperature thereof in an unpolymerized state in advance and then polymerizing the unpolymerized portion by irradiation with light from the upper portion of a mask while the state is maintained when only a specific portion is polymerized by irradiation with ultraviolet rays using a mask.
An optically anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention can be used alone by being peeled off from the substrate or can be used as it is without being peeled off from the substrate. Particularly, since other members are unlikely to be contaminated by the optically anisotropic body, it is useful that the optically anisotropic body is used as a substrate to be laminated or used by being bonded to another substrate.
The retardation film of the present invention contains the optically anisotropic body and the liquid crystalline compound may form a uniform and continuous alignment state with respect to the base material so that the in-plane, the outer plane, both of the in-plane and the outer plane with respect to the base material or the in-plane has biaxiality. Further, an adhesive or an adhesive layer, a pressure sensitive adhesive or a pressure sensitive adhesive layer, a protective film, a polarizing film, or the like may be laminated on the retardation film.
As such a retardation film, for example, the alignment mode of a positive A plate formed by aligning a rod-like liquid crystalline compound substantially horizontally with respect to the base material, a negative A plate formed by aligning a discotic liquid crystalline compound vertically uniaxially with respect to the base material, a positive C plate formed by aligning a rod-like liquid crystalline compound substantially vertically with respect to the base material, a negative C plate formed by aligning a rod-like liquid crystalline compound cholesterically with respect to the base material or aligning a discotic liquid crystalline compound horizontally uniaxially with respect to the base material, a biaxial plate, a positive 0 plate formed by hybrid aligning a rod-like liquid crystalline compound with respect to the base material, or a negative 0 plate formed by hybrid aligning a discotic liquid crystalline compound with respect to the base material can be applied. In the case where the alignment mode thereof is used for a liquid crystal display element, the alignment mode is not particularly limited as long as the mode improves the viewing angle dependence and various alignment modes can be applied.
For example, the alignment mode of a positive A plate, a negative A plate, a positive C plate, a negative C plate, a biaxial plate, a positive 0 plate, or a negative 0 plate can be applied. Among these, it is preferable to use the alignment mode of a positive A plate or a negative C plate. Further, it is more preferable that a positive A plate or a negative C plate is laminated.
Here, a positive A plate refers to an optically anisotropic body in which a polymerizable composition is homogeneously aligned. Further, a negative C plate refers to an optically anisotropic body in which a polymerizable composition is cholesterically aligned.
In a liquid crystal cell for which a retardation film is used, a positive A plate is preferably used as a first retardation layer in order to widen the viewing angle by compensating the viewing angle dependence of polarization axis orthogonality. Here, the positive A plate is a plate in which when the refractive index of the film in an in-plane slow axis direction is set to nx, the refractive index of the film in an in-plane fast axis direction is set to ny, and the refractive index of the film in a thickness direction is set to nz, nx, ny, and nz satisfy a relationship of “nx>ny=nz”. As the positive A plate, a plate in which the in-plane phase difference value at a wavelength of 550 nm is 30 nm to 500 nm is preferable. Further, the thickness direction retardation value is not particularly limited. An Nz coefficient is preferably 0.9 to 1.1.
Further, in order to cancel the birefringence of the liquid crystal molecules, a so-called negative C plate having negative refractive index anisotropy is preferably used as a second retardation layer. Further, a negative C plate may be laminated on a positive A plate.
Here, the negative C plate is a retardation layer in which when the refractive index of the retardation layer in the in-plane slow axis direction is set to nx, the refractive index of the retardation layer in the in-plane fast axis direction is set to ny, and the refractive index of the retardation layer in the thickness direction is set to nz, nx, ny, and nz are in a relationship of “nx=ny>nz”. The thickness direction phase difference value of the negative C plate is preferably 20 to 400 nm.
Further, the refractive index anisotropy in the thickness direction is represented by a thickness direction phase difference value Rth defined by Equation (2). The thickness direction phase difference value Rth can be calculated by acquiring nx, ny, and nz through numerical calculation from Equation (1) and Equations (4) to (7) using an in-plane phase difference value R0, a phase difference value R50 measured by tilting the slow axis as a tilt axis by 50°, a thickness d of the film, and an average refractive index no of the film and then substituting these values in Equation (2). Further, the Nz coefficient can be calculated from Equation (3). Hereinafter, the same applies to other descriptions in the present specification.
R
0=(nx−ny)×d (1)
Rth=[(nx+ny)/2−nz]×d (2)
Nz coefficient=(nx−nz)/(nx−ny) (3)
R
50=(nx−ny′)×d/cos(ϕ) (4)
(nx+ny+nz)/3=n0 (5)
Here,
ϕ=sin−[sin−1(50°)/n0] (6)
ny′=ny×nz/[ny
2×sin2(ϕ)+nz2×cos2 (ϕ)]1/2 (7)
In commercially available phase difference measuring devices, many measuring devices are designed such that the numerical calculation shown here is automatically performed in the devices and the in-plane phase difference value R0, the thickness direction phase difference value Rth, and the like are automatically displayed. Examples of such measuring devices include RETS-100 (manufactured by Otsuka Chemical Co., Ltd.).
The polymerizable composition of the present invention can be used as a lens of the present invention by coating a base material or a base material having an alignment function with the polymerizable composition of the present invention or pouring the polymerizable composition in a lens-shaped mold, uniformly aligning liquid crystal molecules in the polymerizable composition of the present invention in a state in which a nematic phase or a smectic phase is maintained, and then performing polymerization. Examples of the shape of the lens include a simple cell shape, a prism shape, and a lenticular shape.
The polymerizable composition of the present invention can be used as a liquid crystal display element of the present invention by coating a base material or a base material having an alignment function with the polymerizable composition of the present invention, uniformly aligning liquid crystal molecules in the polymerizable composition of the present invention in a state in which a nematic phase or a smectic phase is maintained, and then performing polymerization. As the form of the display element to be used, an optical compensation film, a patterned retardation film of a liquid crystal stereoscopic display element, a retardation correction layer of a color filter, an overcoat layer, and an alignment film for a liquid crystal medium may be exemplified. The liquid crystal display element is formed by interposing at least a liquid crystal medium layer, a TFT drive circuit, a black matrix layer, a color filter layer, a spacer, or an electrode circuit corresponding to the liquid crystal medium layer between at least two base materials. An optical compensation layer, a polarizing plate layer, and a touch panel layer are typically aligned outside the two base materials, but an optical compensation layer, an overcoat layer, a polarizing plate layer, or an electrode layer for a touch panel may be interposed between two base materials in some cases.
Examples of the alignment mode of the liquid crystal display element include a TN mode, a VA mode, an IPS mode, an FFS mode, and an OCB mode. In the case where an optical compensation film or an optical compensation layer is used, a film having a retardation corresponding to the alignment mode can be produced. In the case where a patterned retardation film is used, the liquid crystalline compound in the polymerizable composition may be substantially horizontally aligned with respect to the base material. In the case where an overcoat layer is used, a liquid crystalline compound having a larger number of polymerizable groups in one molecule may be thermally polymerized. In the case where an alignment film for a liquid crystal medium is used, it is preferable to use a polymerizable composition into which a liquid crystalline compound containing an alignment material and a polymerizable group is mixed. Further, a liquid crystalline compound can be mixed with a liquid crystalline medium, and various properties such as the response speed or the contrast can be improved by adjusting the ratio between the liquid crystal medium and the liquid crystalline compound.
The polymerizable composition of the present invention can be used as an organic light-emitting display element of the present invention by coating a base material or a base material having an alignment function with the polymerizable composition of the present invention, uniformly aligning liquid crystal molecules in the polymerizable composition of the present invention in a state in which a nematic phase or a smectic phase is maintained, and then performing polymerization. As the form of the display element to be used, the retardation film and the polarizing plate obtained by the polymerization are combined so as to be used as an anti-reflective film of an organic light-emitting display element. In the case where the combination of the retardation film and the polarizing film is used as an anti-reflective film, the angle between the polarizing axis of the polarizing plate and the slow axis of the retardation film is preferably approximately 45°. The polarizing plate and the retardation film may be bonded to each other using an adhesive or a pressure sensitive adhesive. Further, the retardation film may be directly laminated on the polarizing plate by performing a rubbing treatment or an alignment treatment of laminating a photo-alignment film. The polarizing plate used at this time may be a film form where a dye is doped or a metal form such as a wire grid.
A polymer polymerized in a state in which the polymerizable composition of the present invention is aligned on a nematic phase, a smectic phase, or a base material having an alignment function can be used as a heat radiation material of a lighting element or particularly a light emitting diode element. Examples of the form of the heat radiation material include a prepreg, a polymer sheet, an adhesive, and a sheet provided with metal foil.
The polymerizable composition of the present invention can be used as an optical component of the present invention by performing polymerization in a state in which a nematic phase or a smectic phase is maintained or a state in which the polymerization composition and an alignment material are combined.
The polymerizable composition of the present invention can be also used as a colorant by adding a colorant such as a dye or an organic pigment.
The polymerizable composition of the present invention can be also used as a polarizing film by combining the polymerizable composition with a dichroic dye, lyotropic liquid crystals, or chromonic liquid crystals or adding these to the polymerizable composition.
Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these. Further, “part” and “%” are on a mass basis unless otherwise noted.
24 parts of the compound represented by the formula (1-a-5), 56 parts of the compound represented by the formula (1-a-6), 10 parts of the compound represented by the formula (2-a-1) where n=6, 10 parts of the compound represented by the formula (2-a-1) where n=3, and 0.1 parts of p-methoxyphenol (MEHQ) were added to 400 parts of cyclopentanone (CPN), and then dissolved by heating and stirring at 80° C., and after the dissolution was confirmed, this was restored to room temperature, and 3 parts of Irgacure 907 (Irg907, manufactured by BASF Japan Corporation), and 0.3 parts of the surfactant represented by the formula (H-1) were added thereto and further stirred to give a solution. The solution was transparent and uniform. The resultant solution was filtered through a 0.20-μm membrane filter to give a polymerizable composition (1) of Example 1.
Under the same conditions as those in preparing the polymerizable composition (1) of Example except that the proportions of the compounds shown in the following Tables were changed as in the Tables, polymerizable compositions (2) to (74) of Examples 2 to 66 and 138 to 145, and polymerizable compositions (101) to (115) of Comparative Examples 1 to 15 were prepared.
The following Tables 1 to 7 show the specific formulations of the polymerizable compositions (1) to (74) of the present invention and the comparative polymerizable compositions (101) to (115).
BYK-361N, BYK-333, BYK-331: surfactants manufactured by BYK Japan KK
TEGO GLIDE 432: surfactant manufactured by Evonik Industries Corporation
EFKA-3035: surfactant manufactured by BASF Corporation Chloroform (CLF)
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Re(450 nm)/Re(550 nm) of the compound represented by the above formulae (1-a-5), (1-a-6), (1-a-1), (1-a-2), (1-a-83), (1-a-89), (2-a-1) where n=6, (2-a-1) where n=3, (2-a-31), (2-a-40), (2-a-28), (2-a-11), and (3-a-7) are 0.881, 0.784, 0.716, 0.773, 0.967, 0.664, 0.988, 0.802, 0.900, 0.832, 0.845, 0.806, and 0.850, respectively. Re(450 nm)/Re(550 nm) of the compounds represented by the above formulae (1-b-1) where m11=6 and n11=0, (1-b-27) where m11=6 and n11=2, (2-b-1) where m11=n11=3, and (2-b-2) where m11=n11=4 are 1.075, 1.089, 1.104, and 1.106, respectively.
Re(450 nm)/Re(550 nm) of the compounds represented by the formula (1-a-92), (1-a-93), (1-a-47), (1-a-48), (1-a-49), (1-a-52), (1-a-53), and (1-a-69) are 0.83, 0.85, 0.80, 0.82, 0.81, 0.75, 0.82, and 0.79, respectively.
With respect to Examples 1 to 66 and 138 to 145, and Comparative Examples 1 to 15, the solubility was evaluated as follows.
A: After the preparation, the state of the polymerizable composition of being transparent and uniform was able to be visually confirmed.
B: The state of the polymerizable composition of being transparent and uniform was able to be visually confirmed when the composition was heated and stirred, but precipitation of the compound was confirmed when the temperature was returned to room temperature.
C: The compound was not able to be uniformly dissolved even when heated and stirred.
With respect to each of the polymerizable compositions of Examples 1 to 66 and 138 to 145, and Comparative Examples 1 to 5, the states of the polymerizable composition after the polymerizable composition was allowed to stand for one week at room temperature were visually observed. The evaluation of the storage stability was performed based on the following evaluation criteria.
A: The state of being transparent and uniform was maintained even after the composition was allowed to stand at room temperature for 5 days.
B: The state of being transparent and uniform was maintained even after the composition was allowed to stand at room temperature for 2 days.
C: The precipitation of the compound was confirmed after the composition was allowed to stand at room temperature for 1 hour.
The obtained results are shown in the following tables.
A glass substrate having a thickness of 0.7 mm was coated with a polyimide solution for an alignment film according to a spin coating method, dried at 100° C. for 5 minutes, and then baked at 200° C. for 60 minutes to obtain a coated film. Thereafter, the obtained coated film was subjected to a rubbing treatment. The rubbing treatment was performed using a commercially available rubbing device.
The rubbed base material was coated with the polymerizable composition (1) of the present invention according to a spin coating method and then dried at 80° C. or 100° C. for 2 minutes. The obtained coated film was cooled to room temperature and irradiated with ultraviolet rays at an intensity of 30 mW/cm2 for 30 seconds using a high-pressure mercury lamp, thereby obtaining an optically anisotropic body. On the obtained optically anisotropic body, alignment property evaluation, phase difference ratio, leveling property evaluation, and offset property evaluation were performed according to the following criteria.
A: No defects were found through visual observation and there were no defects found by observation using a polarizing microscope.
B: No defects were found through visual observation, but non-aligned portions were partly present when the observation was made using a polarizing microscope.
C: No defects were found through visual observation, but non-aligned portions were present in the entire composition when the observation was made using a polarizing microscope.
D: Partial defects were found through visual observation, and non-aligned portions were present in the entire composition when the observation was made using a polarizing microscope.
When the phase difference of the obtained optically anisotropic body was measured using a retardation film and optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.), the in-plane phase difference (Re(550)) at a wavelength of 550 nm was 130 nm. Further, the ratio Re(450)/Re(550) of the in-plane phase difference (Re(450)) to the in-plane phase difference Re(550) at a wavelength of 450 nm was 0.854 and a retardation film having reverse wavelength dispersion with excellent uniformity was obtained.
The degree of cissing of the optically anisotropic body was visually observed with a crossed Nicol.
A: No cissing defects were observed on the coating film surface.
B: Extremely few amount of cissing defects were observed on the coating film surface.
C: Small amount of cissing defects were observed on the coating film surface.
D: Large amount of cissing defects were observed on the coating film surface.
TAC film (B) was superimposed on the polymerizable composition surface (A) of the optically anisotropic body and was held at 80° C. for 30 minutes under a load of 40 g/cm2, and then cooled to room temperature while being superimposed. Thereafter, the film (B) was peeled off and visually observed whether or not the surfactant in the polymerizable composition was transferred onto the film (B). In the case where the surfactant has been transferred onto the film (B), it is observed that the part to which the surfactant has been transferred is clouded.
A: No clouded part was observed.
B: Extremely few amount of clouded parts were observed.
C: Small amount of clouded parts were observed.
D: Clouded parts were observed in almost the entire area.
Under the same conditions as in Example 67 except that the polymerizable composition used was changed to the polymerizable compositions (2) to (74) and the comparative polymerizable compositions (101) to (115), respectively, the optically anisotropic bodies of Examples 68 to 132 and 146 to 153, and Comparative Examples 17 to 31 were obtained. The obtained results are shown in the following table.
A photo-alignment film PAM-0021 (manufactured by DIC Corporation) was coated on a 60 μm-thick unstretched cycloolefin polymer film “ZEONOR” (manufactured by Zeon Corporation) by a bar coating method and dried at 80° C. for 2 minutes, and irradiated with polarized UV light of 300 mJ/cm2. The polymerizable composition (56) of the present invention was coated on the photoalignment film by a bar coating method and dried at 80° C. or 100° C. for 2 minutes. After cooling the obtained coating film to room temperature, ultraviolet light was irradiated at a conveyor speed of 6 m/min using a UV conveyor system (manufactured by GS Yuasa Co., Ltd.) to obtain an optically anisotropic body of Example 133. The alignment evaluation, the phase difference ratio, the leveling property evaluation, and the offset evaluation of the obtained optically anisotropic body were carried out in the same manner as in Example 67.
Under the same conditions as in Example 133 except that the polymerizable composition used was changed to the polymerizable compositions (57), (59), (62), and (63) of the present invention, and the comparative polymerizable compositions (102), (104), and (115), respectively, the optically anisotropic bodies of Examples 134 to 137, and Comparative Examples 33 to 35 were obtained. The alignment evaluation, the phase difference ratio, the leveling property evaluation, and the offset evaluation of the obtained optically anisotropic bodies were carried out in the same manner as in Example 67.
It can be said that the polymerizable compositions (1) to (74) of the present invention in Examples 1 to 66 and 138 to 145 are excellent in solubility and storage stability, and that the optically anisotropic bodies formed of the polymerizable compositions of (1) to (66) in Examples 67 to 137 are better than the optically anisotropic bodies formed of the polymerizable compositions (101) to (115) in Comparative Examples 17 to 35 in point of all the evaluation results of alignment performance, leveling performance and offset resistance, and are excellent in productivity.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-229654 | Nov 2015 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/083037 | 11/8/2016 | WO | 00 |
