Re(450)/Re(650)<1.25: Formula (1)
wherein Re(450) and Re(650) are in-plane retardation values (unit: nm) of the optically anisotropic layer at wavelengths of 450 nm and 650 nm, respectively;
0.09<Re—m(550)/d: Formula (2)
wherein Re_m(550) is an in-plane retardation value (unit: nm) of a uniaxial alignment layer in which the director of the liquid crystalline compound is aligned to be parallel in the plane at a wavelength of 550 nm, and d is the thickness of the uniaxial alignment layer (unit: nm).
| 4583825 | Electro-optic display system with improved viewing angle | April, 1986 | Buzak | |
| 5410422 | Gray scale liquid crystal display having a wide viewing angle | April, 1995 | Bos | |
| 5583679 | Liquid crystal display with optical compensatory sheet having discotic molecules varyingly inclined | December, 1996 | Ito et al. | |
| 5646703 | Liquid crystal display | July, 1997 | Kamada et al. | |
| 20060114385 | Liquid crystal display having liquid crystal cell of bend alignment mode or hybrid alignment mode | June, 2006 | Ito et al. | 349/119 |
| DE3911620 | October, 1990 | |||
| JP6214116 | August, 1994 | |||
| JP9197397 | July, 1997 | |||
| JP11316378 | November, 1999 | LIQUID CRYSTAL DISPLAY AND ELLIPTIC POLARIZING PLATE | ||
| JP3056997 | April, 2000 | COLOR LIQUID CRYSTAL DISPLAY DEVICE | ||
| JP2002040429 | February, 2002 | WIDE VIEWING ANGLE LIQUID CRYSTAL DISPLAY DEVICE UTILIZING COMPENSATION FILM | ||
| WO/1996/037804 | November, 1996 | COMPENSATION FILM FOR LIQUID CRYSTAL DISPLAY DEVICE AND OCB MODE LIQUID DISPLAY DEVICE HAVING THE COMPENSATION FILM |
1. An optical film comprising an optically anisotropic layer (1) including a liquid crystalline compound, wherein the optically anisotropic layer (1) satisfies the following formulae (1) and (2):
Re(450)/Re(650)<1.25 Formula (1): wherein Re(450) and Re(650) are in-plane retardation values (unit: nm) of the optically anisotropic layer (1) at wavelengths of 450 nm and 650 nm, respectively;
0.09<Re—m(550)/d Formula (2): wherein Re_m(550) is an in-plane retardation value (unit: nm) of a uniaxial alignment layer in which the director of a liquid crystalline compound constituting the optically anisotropic layer (1) is aligned to be parallel in the plane at a wavelength of 550 nm, and d is the thickness of the uniaxial alignment layer (unit: nm).
2. The optical film according to claim 1, wherein the thickness of the optically anisotropic layer (1) is 1.5 μm or less.
3. The optical film according to claim 1, wherein the liquid crystalline compound constituting the optically anisotropic layer (1) is a discotic liquid crystalline compound.
4. The optical film according to claim 1, wherein the discotic liquid crystalline compound is a polymer of a compound represented by the following formula (DI):
*-(-L21-Q2)n1-L22-L23-Q1 Formula (DI-R): wherein * represents the position to be bonded to H1-H3 sides in the formula (DI), L21 is a single bond or a divalent linking group, L22 represents **—O—, **—O—CO—, **—CO—O—, **—O—CO—O—, **—S—, *—N(R)—, **—CH2—, **—CH═CH— or **—C≡C—, ** represents the position to be bonded to the Q2 side, L23 represents a divalent linking group selected from the group consisting of —O—, —S—, —C(═O)—, —NH—, —CH2—, —CH═CH—, —C≡C— and combinations of these, Q1 represents a polymerizable group or a hydrogen atom, and Q2 represents a divalent group having at least one type of a cyclic structure.
5. The optical film according to claim 1 further comprising an optically anisotropic layer (2), wherein the optically anisotropic layer (2) is a cellulose acylate film.
6. A polarizing plate comprising the optical film according to claim 1 and a polarizing film.
7. The polarizing plate according to claim 6, wherein the optical film comprises a cellulose acylate film.
8. A liquid crystal display device comprising a liquid crystal cell and the polarizing plate according to claim 6.
9. The liquid crystal display device according to claim 8, wherein the polarizing plate comprises a cellulose acylate film.
10. The liquid crystal display device according to claim 8, wherein the liquid crystal cell is of an OCB system.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an optical film, and a polarizing plate and a liquid crystal display device using the same.
2. Description of the Related Art
A liquid crystal display device (LCD) has such large advantages as thin type, lightweight and low power consumption as compared with a CRT (Cathode Ray Tube). The liquid crystal display device is composed of a liquid crystal cell and a pair of polarizing plates arranged on both sides of the liquid crystal cell. The liquid crystal cell is composed of a rod-shaped liquid crystalline compound (liquid crystalline molecule), 2 substrates for sealing the same and electrode layers for applying voltage to the rod-shaped liquid crystalline compound. In order to align the sealed rod-shaped liquid crystalline compound, the 2 substrates are provided with an alignment film. In order to remove color of images displayed on the liquid crystal cell, an optical film (retardation plate) is often arranged between the liquid crystal cell and the polarizing plate. A laminated body of the polarizing plate and the optical film functions as an elliptically polarizing plate. Such function as widening a view angle of the liquid crystal cell is sometimes given to the optical film. A stretched birefringent film has been conventionally used as the optical film.
In place of a stretched birefringent film, use of an optical film having an optically anisotropic layer including a discotic liquid crystalline compound is also proposed (for example, refer to JP-A-6-214116, U.S. Pat. No. 5,583,679, U.S. Pat. No. 5,646,703 and DE-A-3911620). The optically anisotropic layer is formed by aligning a discotic liquid crystalline compound and fixing the aligned stated. A discotic liquid crystalline compound generally has a large birefringent index. In addition, a discotic liquid crystalline compound has multimodal alignment shapes. Accordingly, by using a discotic liquid crystalline compound, it is possible to manufacture an optical film having optical properties that can not be obtained from conventional stretched birefringent films.
There is proposed a liquid crystal display device using a liquid crystal cell of a bend alignment mode in which rod-shaped liquid crystalline compounds are aligned in substantially opposite directions (symmetrically) in the upper portion and the lower portion of the liquid crystal cell (for example, refer to U.S. Pat. No. 4,583,825 and U.S. Pat. No. 5,410,422). Since rod-shaped liquid crystalline compounds are aligned symmetrically in the upper portion and the lower portion of the liquid crystal cell, the liquid crystal cell of the bend alignment mode has a self-optical compensatory function. Consequently, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. A liquid crystal display device of the bend alignment mode has such advantage as quick response speed.
The bend alignment mode has such characteristics as a wide view angle and quick response speed as compared with general liquid crystal modes (TN mode, STN mode). However, when compared with a CRT, a further improvement is necessary. In order to further improve a liquid crystal display device of a bend alignment mode, use of an optical film is considered as is the case for general liquid crystal modes. However, conventional optical films composed of a stretched birefringent film were insufficient in an optical compensatory function for a liquid crystal display device of the bend alignment mode. As described above, in place of a stretched birefringent film, use of an optical film having an optically anisotropic layer including a discotic liquid crystalline compound and a support is proposed. Further, liquid crystal display devices of the bend alignment mode using an optical film including a discotic liquid crystalline compound are also proposed (for example, refer to JP-A-9-197397 and WO 96/37804). By using an optical film including a discotic liquid crystalline compound, the view angle of a liquid crystal display device of the bend alignment mode is significantly improved.
Such problem is indicated that, when an optical film including a discotic liquid crystalline compound is used for a liquid crystal display device of the bend alignment mode, light with a specific wavelength leaks to color the displayed image (for example, refer to JP-A-11-316378). There is described that this coloring is caused by wavelength dependence of the transmittance of an elliptically polarizing plate (laminated body of a polarizing film and an optical film). Since wavelength dependence of the anisotropy of a liquid crystalline compound used for a liquid crystal cell differs from wavelength dependence of the anisotropy of an optical film (for example, discotic liquid crystal), light with a short wavelength (blue) generally leaks in a liquid crystal display device of the bend alignment mode. However, by matching the chromatic dispersion of a liquid crystalline compound with that of an optical film (discotic liquid crystal), hue at the time of black level is improved.
And it is reported that, by arranging an optically anisotropic layer and a polarizing film so that an angle between an average direction of an orthogonal projection of the normal line of the disc plane of the discotic liquid crystalline compound onto the optically anisotropic layer and the in-plane transmission axis of the polarizing film substantially is 45°, the largest optical compensatory effect for a liquid crystal cell of the bend alignment mode can be obtained. With regard to a bend alignment liquid crystal device using an optical film including a discotic liquid crystalline compound, various methods have been proposed to lower hue alteration and prevent gradation reversal (for example, refer to Japanese Patent No. 3056997 and JP-A-2002-40429).
SUMMARY OF THE INVENTION
However, even when an optical compensatory sheet including a discotic liquid crystalline compound is used, it was difficult to prevent gradation reversal while satisfying contrast property, view angle property and hue in a bend alignment liquid crystal device. Further, in order to solve the problem, a large amount of elements used for an optical film became necessary, to lead to push up the cost.
The purpose of the present invention is to provide an optical film and a polarizing plate capable of appropriately optically compensating a liquid crystal cell, in particular a liquid crystal cell of a bend alignment mode, and further, to lower cost by reducing the use amount of elements of the optical film; and to provide a liquid crystal display device with a low cost for displaying good images having high contrast, excellent view angle property, no problem of hue at the time of black level and, in addition, generating no gradation reversal, by using such optical film to significantly lower transmittance of the front side and in polar angle directions of left, right, top and bottom at the time of black level, and by controlling wave distribution property of a discotic liquid crystalline compound for use in the optical film.
The purpose of the invention was achieved through the following (1)-(7).
(1) An optical film having an optically anisotropic layer ( 1 ) including a liquid crystalline compound, wherein the optically anisotropic layer ( 1 ) satisfies the following formulae (1) and (2):
Re (450)/ Re (650)<1.25 Formula (1):
wherein Re(450) and Re(650) are in-plane retardation values (unit: nm) of the optically anisotropic layer ( 1 ) at wave lengths of 450 nm and 650 nm, respectively;
0.09 <Re — m (550)/ d Formula (2):
wherein Re_m(550) is an in-plane retardation value (unit: nm) of a uniaxial alignment layer in which the director of a liquid crystalline compound constituting the optically anisotropic layer ( 1 ) is aligned to be parallel in the plane at a wavelength of 550 nm, and d is the thickness of the uniaxial alignment layer (unit: nm).
(2) The optical film described in (1), wherein the thickness of the optically anisotropic layer ( 1 ) is 1.5 μm or less.
(3) The optical film described in (1) or (2), wherein the liquid crystalline compound constituting the optically anisotropic layer ( 1 ) is a discotic liquid crystalline compound.
(4) The optical film described in any of (1)-(3) further including an optically anisotropic layer ( 2 ), wherein the optically anisotropic layer ( 2 ) is a cellulose acylate film.
(5) A polarizing plate having the optical film described in any of (1)-(4) and a polarizing film.
(6) A liquid crystal display device having a liquid crystal cell and the polarizing plate described in (5).
(7) The liquid crystal display device described in (6), wherein the liquid crystal cell is of an OCB system.
According to the invention, it becomes possible to provide an optical film that appropriately optically compensates a liquid crystal cell, in particular a liquid crystal cell of a bend alignment mode, and is thin. Further, by satisfying the property of the invention, it becomes possible to reduce the use amount of a liquid crystal compound when manufacturing the optical film, thereby providing an optical film with a low cost. Furthermore, by adopting such optical film, it becomes possible to provide a liquid crystal display device that has a significantly lowered transmittance of the front side and in polar angle directions of left, right, top and bottom at the time of black level, and displays good images having high contrast, excellent view angle property, no problem of hue at the time of black level, and generating no gradation reversal.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional drawing schematically showing the alignment of a liquid crystalline compound in a bend alignment liquid crystal cell.
FIG. 2 is a schematic drawing showing a polarizing plate.
FIG. 3 is a schematic drawing showing a bend alignment type liquid crystal display device according to the present invention.
FIG. 4 is a cross-sectional schematic drawing showing a typical shape of an optical diffusion film.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the content of the present invention will be described in detail. In this connection, “-” in the present description is used in such meaning that the numerical values described before and after “-” are included as the lower limit and the upper limit respectively.
Further, in the present description, Re(λ) and Rth(λ) represent in-plane retardation and retardation in a thickness direction, respectively, at a wavelength of λ. Re(λ) is measured by irradiating light having a wavelength of λ nm in a normal direction of a film in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth(λ) is calculated by KOBRA 21ADH on the basis of retardation values measured in total 3 directions, that is, the aforementioned Re(λ), a retardation value measured by irradiating light having a wavelength of λ nm from a direction tilted by +40° relative to a film normal direction while taking an in-plane slow phase axis (judged by KOBRA 21ADH) as a tilt axis (rotation axis), and a retardation value measured by irradiating light having a wavelength of λ nm from a direction tilted by −40° relative to a film normal direction while taking an in-plane slow phase axis as a tilt axis (rotation axis), a presumptive value of an average refractive index and an input film thickness value. Here, as a presumptive value of an average refractive index, values in Polymer Handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. For a material whose average refractive index is not known, it can be measured with an Abbe refractometer. Average values of refractive index of prevailing optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), and polystyrene (1.59). By inputting a presumptive value of the average refractive index and a film thickness, KOBRA 21ADH calculates nx, ny and nz. From the calculated nx, ny and nz, Nz=(nx−nz)/(nx−ny) is further calculated.
(Liquid Crystal Display Device)
FIG. 1 is a cross-sectional view schematically showing alignment of a liquid crystalline compound in a bend alignment liquid crystal cell. As shown in FIG. 1, a bend alignment liquid crystal cell has such structure that a liquid crystalline compound ( 11 ) is sealed between an upside substrate ( 14 a ) and a downside substrate ( 14 b ). The liquid crystalline compound ( 11 ) for use in a bend alignment liquid crystal cell generally has a positive permittivity anisotropy. The upside substrate ( 14 a ) and the downside substrate ( 14 b ) of the liquid crystal cell have alignment films ( 12 a , 12 b ) and electrode layers ( 13 a , 13 b ) respectively. The alignment film has a function for aligning rod-shaped liquid crystalline compounds ( 11 a - 11 j ). RD is a rubbing direction of the alignment film. The electrode layer has a function for applying voltage to the rod-shaped liquid crystalline compounds ( 11 a - 11 j ).
When the applied voltage to the bend alignment liquid crystal cell is low, as denoted by “off” in FIG. 1, the rod-shaped liquid crystalline compounds ( 11 a - 11 e ) on the upper substrate ( 14 a ) side of the liquid crystal cell and the rod-shaped liquid crystalline compounds ( 11 f - 11 j ) on the lower substrate ( 14 b ) side align in a reverse direction (vertically symmetrically) to each other. Further, the rod-shaped liquid crystalline compounds ( 11 a , 11 b , 11 i , 11 j ) near the substrates ( 14 a , 14 b ) align in an approximately horizontal direction, and the rod-shaped liquid crystalline compounds ( 11 d - 11 g ) at the central region align in an approximately vertical direction, in the liquid crystal cell.
As denoted by “on” in FIG. 1, when an applied voltage is high, the rod-shaped liquid crystalline compounds ( 11 a , 11 j ) near the substrates ( 14 a , 14 b ) remain in an approximately horizontally aligned state. On the other hand, the rod-shaped liquid crystalline compounds ( 11 e , 11 f ) at the liquid crystal cell central region remain in an approximately vertically aligned state. The rod-shaped liquid crystalline compounds whose alignment alter through the increase in the voltage are those ( 11 b , 11 c , 11 d , 11 g , 11 h , 11 i ) being located in the intermediate portion between the substrate and the liquid crystal cell central region, and these align more vertically than in the “off ” state. However, the state in which rod-shaped liquid crystalline compounds ( 11 a - 11 e ) on the upper substrate ( 14 a ) side of the liquid crystal cell and rod-shaped liquid crystalline compounds ( 11 f - 11 j ) on the lower substrate( 14 b ) side align in an inverse direction (vertically symmetrically) is the same as the “off” state.
FIG. 2 is a schematic drawing showing a polarizing plate. The polarizing plate shown in FIG. 2 is composed of a laminated body of an optically anisotropic layer ( 1 ) ( 31 ) including discotic liquid crystalline compounds ( 31 a - 31 e ), an optically anisotropic layer ( 2 ) including at least one cellulose acylate film, and a polarizing film ( 34 ). The polarizing plate shown in FIG. 2 has an alignment film ( 32 ) between the optically anisotropic layer ( 1 ) ( 31 ) and the optically anisotropic layer ( 2 ) ( 33 ). The discotic liquid crystalline compounds ( 31 a - 31 e ) of the optically anisotropic layer ( 1 ) ( 31 ) are a planer molecule. The discotic liquid crystalline compounds ( 31 a - 31 e ) have only one plane, that is, discotic plane in the molecule. The discotic plane tilts relative to the plane of the optically anisotropic layer ( 2 ) ( 33 ). The angle (tilt angle) between the discotic plane and the optically anisotropic layer ( 2 ) increases along with the increase in the distance of the discotic liquid crystalline compound from the alignment film. An average tilt angle is preferably within a range of 15-50°. When the tilt angle is altered as shown in FIG. 2, a view angle-expanding function of the polarizing plate is significantly enhanced. In addition, a polarizing plate whose tilt angle has been altered also has such function as preventing reversal, graduation alteration, or coloring of displayed images. An average of directions (PL) of orthogonally projected normal lines (NL) of the discotic plane of discotic liquid crystalline compounds ( 31 a - 31 e ) onto the optically anisotropic layer ( 2 ) ( 33 ) is inversely parallel relative to the rubbing direction (RD) of the alignment film ( 32 ).
In a preferable embodiment of the invention, the angle between the average direction of orthogonally projected normal lines of the discotic plane of discotic liquid crystalline compounds onto the optically anisotropic layer ( 2 ) ( 33 ) and the in-plane slow phase axis (SA) of the optically anisotropic layer ( 2 ) ( 33 ) is set to substantially 45°. Consequently, in a manufacturing process of the polarizing plate, it suffices to adjust so that an angle (θ) between the rubbing direction (RD) of the alignment film ( 32 ) and the in-plane slow phase axis (SA) of the optically anisotropic layer ( 2 ) becomes substantially 45°. In the invention, furthermore, the optically anisotropic layer ( 2 ) and the polarizing film are arranged so that the in-plane slow phase axis (SA) of the optically anisotropic layer ( 2 ) and the in-plane transmission axis (TA) of the polarizing film ( 34 ) become substantially parallel or substantially vertical to each other. In the polarizing plate shown in FIG. 2, one optically anisotropic layer ( 2 ) is arranged parallel. The in-plane slow phase axis (SA) of the optically anisotropic layer ( 2 ) ( 33 ) corresponds in principle to the stretching direction of the optically anisotropic layer ( 2 ). The in-plane transmission axis (TA) of the polarizing film ( 34 ) corresponds in principle to the direction perpendicular to the stretching direction of the polarizing film.
FIG. 3 is a schematic drawing showing the bend alignment type liquid crystal display device according to the invention. The liquid crystal display device shown in FIG. 3 is composed of a bend alignment liquid crystal cell ( 10 ), a pair of polarizing plates ( 31 A, 33 A, 34 A, 31 B, 33 B, 34 B) arranged on both sides of the liquid crystal cell, and a backlight (BL). The bend alignment liquid crystal cell ( 10 ) corresponds to the liquid crystal cell shown in FIG. 1. The rubbing directions (RD 2 , RD 3 ) of the upper and lower sides of the liquid crystal cell ( 10 ) are the same (parallel). In the polarizing plate, the optically anisotropic layers ( 1 ) ( 31 A, 31 B), the optically anisotropic layers ( 2 ) ( 33 A, 33 B) and the polarizing films ( 34 A, 34 B) are laminated in this order from the liquid crystal cell ( 10 ) side. The rubbing directions (RD 1 , RD 4 ) of the discotic liquid crystalline compound of the optically anisotropic layers ( 1 ) ( 31 A, 31 B) are inversely parallel relative to the rubbing directions (RD 2 , RD 3 ) of the facing liquid crystal cell. As described above, the rubbing directions (RD 1 , RD 4 ) of the discotic liquid crystalline compounds are inversely parallel to an average direction of the orthogonally projected normal line of the discotic plane onto the optically anisotropic layer ( 2 ). The in-plane slow phase axes (SA 1 , SA 2 ) of the optically anisotropic layers ( 2 ) ( 33 A, 33 B) and the in-plane transmission axes (TA 1 , TA 2 ) of the polarizing films ( 34 A, 34 B) substantially form an angle of 45° relative to the rubbing directions (RD 1 , RD 4 ) of the discotic liquid crystalline compound in the same plane. The two polarizing films ( 34 A, 34 B) are arranged so that the in-plane transmission axes (TA 1 , TA 2 ) are orthogonal to each other (crossed nicols).
(Optically Anisotropic Layer ( 1 ))
The optically anisotropic layer ( 1 ) of the invention includes a liquid crystalline compound. The optically anisotropic layer ( 1 ) may be formed directly on the surface of the optically anisotropic layer ( 2 ), or may be formed on an alignment film or the like having been formed on the optically anisotropic layer ( 2 ).
As a liquid crystalline compound for use in the optically anisotropic layer ( 1 ), either of a rod-shaped liquid crystalline compound and a discotic liquid crystalline compound can be preferably adopted, but a discotic liquid crystalline compound is preferable. A retardation value measured from the film normal direction of the optically anisotropic layer ( 1 ) is preferably 20-40 nm, and more preferably 25-40 nm.
The optically anisotropic layer ( 1 ) is preferably designed so that it compensates the liquid crystalline compound in the liquid crystal cell at the time of black level of a liquid crystal display device. With regard to an alignment state of a liquid crystalline compound in a liquid crystal cell, there is description in IDW′00, FMC7-2, P 411-414.
(Discotic Liquid Crystalline Compound)
A discotic liquid crystalline compound in the invention may be a high-molecular liquid crystal or a low-molecular liquid crystal, and, further, a cross-linked low-molecular liquid crystal that no longer shows liquid crystalline property is also included.
The discotic liquid crystalline compound in the invention includes benzene derivatives described in a study report of C. Destrade et al., Mol. Cryst. vol 71, p 111 (1981); truxene derivatives described in study reports of C. Destrade et al., Mol. Cryst, vol. 122, p 141 (1985), and Physics Lett, A, vol. 78, p 82 (1990); cyclohexane derivatives described in a study report of B. Kohne et al., Angew. Chem. vol. 96, p 70 (1984); and azacrown-based and phenylacetylene-based macrocycles described in study reports of J. M. Lehn et al., J. Chem. Commun., p 1794 (1985) and J. Zhang et al., J. Am. Chem. Soc, vol. 116, p 2655 (1994).
The above-described discotic liquid crystalline compound includes such compounds that represent liquid crystalline properties, the compound having a structure in which, to the center mother nucleus of the molecule, straight chain alkyl groups or alkoxy groups, or substituted benzoyloxy groups are radially substituted as the side chains of the mother nucleus. The preferable compound is that the molecule or the aggregate of molecules has rotational symmetric property to be capable of giving a certain alignment.
When the optically anisotropic layer ( 1 ) is formed from a discotic liquid crystalline compound, the compound finally included in the optically anisotropic layer ( 1 ) is not required anymore to show liquid crystalline property. For example, in the case where a low molecular weight discotic liquid crystalline compound has a group capable of reacting by heat or light, and the group reacts by heat or light to polymerize or cross-link and increase in a molecular weight thereof, to result in forming the optically anisotropic layer ( 1 ), the compound included in the optically anisotropic layer ( 1 ) may have already lost liquid crystalline property. Preferable examples of the discotic liquid crystalline compound are described in JP-A-8-50206. Polymerization of a discotic liquid crystalline compound is described in JP-A-8-27284.
In order to fix a discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group to a discotic core of the discotic liquid crystalline compound as a substituent. In this connection, a direct bonding of a polymerizable group to the discotic core makes it difficult to keep an alignment state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. Accordingly, the discotic liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula (DI).
wherein Y 11 , Y 12 and Y 13 each independently represents methine or a nitrogen atom.
When each of Y 11 , Y 12 and Y 13 is methane, a hydrogen atom of methine may have been substituted by a substituent. Here, methine means an atom group obtained by removing 3 hydrogen atoms from methane.
Preferable examples of the substituent that may be had by the carbon atom of methine include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom and a cyano group. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, and an alkyl group having 1-12 carbon atoms, an alkoxy group having 1-12 carbon atoms, an alkoxycarbonyl group having 2-12 carbon atoms, an acyloxy group having 2-12 carbon atoms, a halogen atom and cyano group are further preferable. More preferably each of Y 11 , Y 12 and Y 13 is methine, and further preferably the methine has no substituent.
In the formula (DI), L 1 , L 2 and L 3 each independently represents a single bond or a divalent linking group. When L 1 , L 2 and L 3 are divalent linking groups, preferably each independently represents a divalent linking group selected from the group consisting of —O—, —S—, —C(═O)—, —NR 7 —, —CH═CH—, —C≡C—, a divalent cyclic group and combinations of these. The R 7 is an alkyl group having 1-7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1-4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and most preferably a hydrogen atom.
The divalent cyclic group in L 1 , L 2 and L 3 means a divalent linking group having at least one type of cyclic structure (hereinafter, it may be referred to as a cyclic group). The cyclic group preferably has a 5-membered, 6-membered or 7-membered ring, more preferably a 5-membered or 6-membered ring, and further preferably a 6-membered ring. A ring included in the cyclic group may be a condensed ring, but a single ring is preferred to a condensed ring. A ring included in the cyclic group may be any of an aromatic ring, an aliphatic ring and a heterocyclic ring. Preferable examples of the aromatic ring include a benzene ring and a naphthalene ring. Preferable example of the aliphatic ring includes a cyclohexane ring. Preferable examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring. As the cyclic group, an aromatic ring or a heterocyclic ring is more preferable. The cyclic group is more preferably a divalent linking group consisting of a ring structure alone (but may include a substituent).
Among the divalent cyclic groups represented by L 1 , L 2 and L 3 , as a cyclic group having a benzene ring, a 1,4-phenylene group is preferable. As a cyclic group having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. As a cyclic group having a cyclohexane ring, a 1,4-cyclohexylene group is preferable. As a cyclic group having a pyridine ring, a pyridine-2,5-diyl group is preferable. As a cyclic group having a pyrimidine ring, a pyrimidine-2,5-diyl group is preferable.
The divalent cyclic group represented by L 1 , L 2 and L 3 may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1-16 carbon atoms, an alkenyl group having 2-16 carbon atoms, an alkynyl group having 2-16 carbon atoms, a halogen-substituted alkyl group having 1-16 carbon atoms, an alkoxy group having 1-16 carbon atoms, an acyl group having 2-16 carbon atoms, an alkylthio group having 1-16 carbon atoms, an acyloxy group having 2-16 carbon atoms, an alkoxycarbonyl group having 2-16 carbon atoms, a carbamoyl group, a carbamoyl group substituted by an alkyl group having 2-16 carbon atoms, and an acylamino group having 2-16 carbon atoms.
Preferable examples of L 1 , L 2 and L 3 include a single bond, *—O—CO—, *—CO—O—, *—CH═CH—, *—C≡C—, *-divalent cyclic group-, *—O—CO-divalent cyclic group-, *—CO—O-divalent cyclic group-, *—CH═CH-divalent cyclic group-, *—C≡C-divalent cyclic group-, *-divalent cyclic group-O—CO—, *-divalent cyclic group-CO—O—, *-divalent cyclic group-CH═CH— and *-divalent cyclic group-C≡C—. Among these, a single bond, *—CH═CH—, *—C≡C—, *-divalent cyclic group-O—CO—, *—CH═CH-divalent cyclic group- and *—C≡C-divalent cyclic group- are more preferable, and a single bond is further preferable. Here, * represents the position to be bonded to a 6-membered ring side including Y 11 , Y 12 and Y 13 in formula (DI).
H 1 , H 2 and H 3 each independently represents the following formula (DI-A) or the following formula (DI-B).
wherein YA 1 and YA 2 each independently represents methine or a nitrogen atom. Preferably at least one of YA 1 and YA 2 is a nitrogen atom, and more preferably both of YA 1 and YA 2 are nitrogen atoms. XA represents an oxygen atom, a sulfur atom, methylene or imino, wherein an oxygen atom is preferable. * represents a position to be bonded to L 1 -L 3 sides in the formula (DI), and ** represents a position to be bonded to R 1 -R 3 sides in the formula (DI). Here, imino means a group represented by —NH— (including one in which H is substituted by a substituent).
wherein YB 1 and YB 2 each independently represents methine or a nitrogen atom. Preferably at least one of YB 1 and YB 2 is a nitrogen atom, and more preferably both are nitrogen atoms. XB represents an oxygen atom, a sulfur atom, methylene or imino, wherein an oxygen atom is preferable. * represents the position to be bonded to L 1 -L 3 sides in the formula (DI), and ** represents the position to be bonded to R 1 -R 3 sides in the formula (DI).
R 1 , R 2 and R 3 each independently represents the following formula (DI-R).
*-(-L 21 -Q 2 ) n1 -L 22 -L 23 -Q 1 Formula (DI-R):
wherein * represents the position to be bonded to H 1 -H 3 sides in the formula (DI).
L 21 is a single bond or a divalent linking group. When L 21 is a divalent linking group, it is preferably a divalent linking group selected from the group consisting of —O—, —S—, —C(═O)—, —NR 7 —, —CH═CH—, —C≡C— and combinations of these. R 7 is an alkyl group having 1-7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1-4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and most preferably a hydrogen atom.
L 21 is preferably any one of a single bond, ***—O—CO—, ***—CO—O—, ***—CH═CH— and ***—C≡C— (here, *** represents the * side in the formula (DI-R)), and more preferably a single bond.
Q 2 represents a divalent group (cyclic group) having at least one type of a cyclic structure. With regard to such cyclic group, a cyclic group having a 5-membered, 6-membered or 7-membered ring is preferable, a cyclic group having a 5-membered or 6-membered ring is more preferable, and a cyclic group having a 6-membered ring is further preferable. The ring included in the cyclic group may be a condensed ring, but a single ring is preferred to a condensed ring. Further, a ring included in the cyclic group may be any one of an aromatic ring, an aliphatic ring and a heterocyclic ring. Preferable examples of the aromatic ring include a benzene ring and a naphthalene ring. Preferable example of the aliphatic ring includes a cyclohexane ring. Preferable examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring. As the cyclic group, an aromatic ring or a heterocyclic ring is more preferable. The cyclic group is more preferably a divalent linking group consisting of a ring structure alone (but may include a substituent).
Among the above-described Q 2 , as a cyclic group having a benzene ring, a 1,4-phenylene group is preferable. As a cyclic group having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. As a cyclic group having a cyclohexane ring, a 1,4-cyclohexylene group is preferable. As a cyclic group having a pyridine ring, a pyridine-2,5-diyl group is preferable. As a cyclic group having a pyrimidine ring, a pyrimidine-2,5-diyl group is preferable. Among these, in particular, a 1,4-phenylene group and a 1,4-cyclohexylene group are preferable.
Q 2 may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a nitro group, an alkyl group having 1-16 carbon atoms, an alkenyl group having 2-16 carbon atoms, an alkynyl group having 2-16 carbon atoms, a halogen-substituted alkyl group having 1-16 carbon atoms, an alkoxy group having 1-16 carbon atoms, an acyl group having 2-16 carbon atoms, an alkylthio group having 1-16 carbon atoms, an acyloxy group having 2-16 carbon atoms, an alkoxycarbonyl group having 2-16 carbon atoms, a carbamoyl group, a carbamoyl group substituted by an alkyl group having 2-16 carbon atoms and an acylamino group having 2-16 carbon atoms. Among these, a halogen atom, a cyano group, an alkyl group having 1-6 carbon atoms and a halogen-substituted alkyl group having 1-6 carbon atoms are preferable, a halogen atom, an alkyl group having 1-4 carbon atoms and a halogen-substituted alkyl group having 1-4 carbon atoms are more preferable, and a halogen atom, an alkyl group having 1-3 carbon atoms and a trifluoromethyl group are further preferable.
n1 represents 0 or an integer of 1-4. As n1, an integer of 1-3 is preferable, and 1 or 2 is more preferable.
L 22 represents **—O—, **—O—CO—, **—CO—O—, **—O—CO—O—, **—S—, *—N(R)—, **—CH 2 —, **—CH═CH— or **—C≡C—, and ** represents the position to be bonded to the Q 2 side.
L 22 is preferably **—O—, **—O—CO—, **—CO—O—, **—O—CO—O—, **—CH 2 —, **—CH═CH— or **—C≡C—, and more preferably **—O—, **—O—CO—, **—O—CO—O— or **—CH 2 —.
L 23 represents a divalent linking group selected from the group consisting of —O—, —S—, —C(═O)—, —NH—, —CH 2 —, —CH═CH—, —C≡C— and combinations of these. Here, a hydrogen atom of —NH—, —CH 2 — and —CH═CH— may be substituted by a substituent. Preferable examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1-6 carbon atoms, a halogen-substituted alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms, an acyl group having 2-6 carbon atoms, an alkylthio group having 1-6 carbon atoms, an acyloxy group having 2-6 carbon atoms, an alkoxycarbonyl group having 2-6 carbon atoms, a carbamoyl group, a carbamoyl group substituted by an alkyl having 2-6 carbon atoms and an acylamino group having 2-6 carbon atoms, and more preferable ones include a halogen atom and an alkyl group having 1-6 carbon atoms.
L 23 is preferably selected from the group consisting of —O—, —C(═O)—, —CH 2 —, —CH═CH—, —C≡C— and combinations of these. L 23 preferably contains 1-20 carbon atoms, and more preferably 2-14 carbon atoms. Further, L 23 preferably contains 1-16 —CH 2 —, and more preferably 2-12 —CH 2 —.
Q 1 represents a polymerizable group or a hydrogen atom. When the liquid crystalline compound used in the invention is used for an optical film and the like wherein magnitude of retardation preferably does not alter by heat, Q 1 is preferably a polymerizable group. The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of an addition polymerization reaction or a condensation polymerization reaction. Examples of the polymerizable group are shown below.
Further, the polymerizable group is particularly preferably a functional group capable of an addition polymerization reaction. Preferable examples of the polymerizable group include a polymerizable ethylenic unsaturated group and a ring-opening polymerizable group.
Examples of the polymerizable ethylenic unsaturated group include the following formulae (M-1)-(M-6).
In formulae (M-3), (M-4), R represents a hydrogen atom or an alkyl group, wherein a hydrogen atom or a methyl group is preferable.
Among the formulae (M-1)-(M-6), (M-1) or (M-2) is preferable, and (M-1) is more preferable.
The ring-opening polymerizable group is preferably a cyclic ether group, more preferably an epoxy group or an oxetanyl group, and most preferably an epoxy group.
As the liquid crystalline compound for use in the invention, a liquid crystalline compound represented by the following formula (DII) is particularly preferable.
wherein Y 31 , Y 32 and Y 33 each independently represents methine or a nitrogen atom, having the same meaning and also the same preferable range as Y 11 , Y 12 and Y 13 in the formula (DI).
In the formula (DII), R 31 , R 32 and R 33 each independently represents the following formula (DII-R).
wherein A 31 and A 32 each independently represents methine or a nitrogen atom, wherein preferably at least one is a nitrogen atom, and more preferably both are nitrogen atoms. X 3 represents an oxygen atom, a sulfur atom, methylene or imino, wherein an oxygen atom is preferable.
Q 31 represents a divalent linking group having a 6-membered cyclic structure (hereinafter, it may be referred to as a 6-membered cyclic group). The 6-membered ring may be a condensed ring, but a single ring is more preferred to a condensed ring. Further, a ring included in a 6-membered cyclic group may be any one of an aromatic ring, an aliphatic ring and a heterocyclic ring. Preferable examples of the aromatic ring include a benzene ring and a naphthalene ring. A preferable example of the aliphatic ring includes a cyclohexane ring. Preferable examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring. Q 31 is preferably a divalent linking group consisting of a 6-membered cyclic structure alone (but it may have a substituent).
Among Q 31 , as a 6-membered cyclic group having a benzene ring, a 1,4-phenylene group and a 1,3-phenylene group are preferable. As a ring structure having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. As a ring structure having a cyclohexane ring, a 1,4-cyclohexylene group is preferable. As a ring structure having a pyridine ring, a pyridine-2,5-diyl group is preferable. As a ring structure having a pyrimidine ring, a pyrimidine-2,5-diyl group is preferable. Among these, in particular, a 1,4-phenylene group and a 1,3-phenylene group are more preferable.
The ring structure of Q 31 may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a nitro group, an alkyl group having 1-16 carbon atoms, an alkenyl group having 2-16 carbon atoms, an alkynyl group having 2-16 carbon atoms, a halogen atom-substituted alkyl group having 1-16 carbon atoms, an alkoxy group having 1-16 carbon atoms, an acyl group having 2-16 carbon atoms, an alkylthio group having 1-16 carbon atoms, an acyloxy group having 2-16 carbon atoms, an alkoxycarbonyl group having 2-16 carbon atoms, a carbamoyl group, a carbamoyl group substituted by an alkyl having 2-16 carbon atoms and an acylamino group having 2-16 carbon atoms. As a substituent for a 6-membered cyclic group, a halogen atom, a cyano group, an alkyl group having 1-6 carbon atoms or a halogen atom-substituted alkyl group having 1-6 carbon atoms is preferable, a halogen atom, an alkyl group having 1-4 carbon atoms or a halogen atom-substituted alkyl group having 1-4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1-3 carbon atoms or a trifluoromethyl group is further preferable.
n3 represents an integer of 1-3, wherein 1 or 2 is preferable.
L 31 represents *—O—, *—O—CO—, *—CO—O—, *—O—CO—O—, *—S—, —N(R)—, *—CH 2 —, *—CH═CH— or *—C≡C—, * represents the position to be bonded to the Q 31 side, specifically having the same meaning and also the same preferable range as L 22 in the formula (DI-R).
L 32 represents a divalent linking group selected from the group consisting of —O—, —S—, —C(═O)—, —NH—, —CH 2 —, —CH═CH—, —C≡C— and combination of these, specifically having the same meaning and also the same preferable range as L 23 in the formula (DI-R).
Q 32 in the formula (DII-R) represents a polymerizable group or a hydrogen atom, specifically having the same meaning and also the preferable range as Q 1 in the formula (DI-R).
Specific examples of the liquid crystalline compound represented by the formula (DI) are shown below. However, the invention is not intended to be restricted to these.
| | ||||
| R = | | X = | —OC 4 H 9 | D-1 |
| —OC 5 H 11 | D-2 | |||
| —OC 6 H 13 | D-3 | |||
| —OC 7 H 15 | D-4 | |||
| —OC 8 H 17 | D-5 | |||
| —OCH 2 CH(CH 3 )C 4 H 9 | D-6 | |||
| —O(CH 2 ) 2 OCOCH═CH 2 | D-7 | |||
| —O(CH 2 ) 3 OCOCH═CH 2 | D-8 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-9 | |||
| —O(CH 2 ) 5 OCOCH═CH 2 | D-10 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-11 | |||
| —O(CH 2 ) 7 OCOCH═CH 2 | D-12 | |||
| —O(CH 2 ) 8 OCOCH═CH 2 | D-13 | |||
| —O(CH 2 ) 2 CH(CH 3 )OCOCH═CH 2 | D-14 | |||
| —O(CH 2 ) 3 CH(CH 3 )OCPCH═CH 2 | D-15 | |||
| —O(CH 2 CH 2 O)CHOCH═CH 2 | D-16 | |||
| | D-17 | |||
| —O(CH 2 ) 4 OCOCH═CHCH 3 | D-18 | |||
| —OCH═CH 2 | D-19 | |||
| | D-20 | |||
| —OCOC 4 H 9 | D-21 | |||
| —OCOC 5 H 11 | D-22 | |||
| —OCOC 6 H 13 | D-23 | |||
| —OCO(CH 2 ) 2 OCOCH═CH 2 | D-24 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-25 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-26 | |||
| —OCO(CH 2 ) 5 OCOCH═CH 2 | D-27 | |||
| —OCO(CH 2 ) 6 OCOCH═CH 2 | D-28 | |||
| —OCO(CH 2 ) 7 OCOCH═CH 2 | D-29 | |||
| —OCO(CH 2 ) 2 CH(CH 3 )OCOCH═CH 2 | D-30 | |||
| | D-31 | |||
| —OCO(CH 2 ) 2 OCOCH═CHCH 3 | D-32 | |||
| —OCO(CH 2 ) 4 OCH═CH 2 | D-33 | |||
| | D-34 | |||
| —OCOOC 4 H 9 | D-35 | |||
| —OCOOC 5 H 11 | D-36 | |||
| —OCOOC 6 H 13 | D-37 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-38 | |||
| —OCOO(CH 2 ) 3 OCOCH═CH 2 | D-39 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-40 | |||
| —OCOO(CH 2 ) 5 OCOCH═CH 2 | D-41 | |||
| —OCOO(CH 2 ) 6 OCOCH═CH 2 | D-42 | |||
| —OCOO(CH 2 ) 7 OCOCH═CH 2 | D-43 | |||
| —OCOOCH(CH 3 )CH 2 CH 2 OCOCH═CH 2 | D-44 | |||
| —OCOOCH(CH 2 CH 2 O) 2 COCH═CH 2 | D-45 | |||
| | D-46 | |||
| —OCOO(CH 2 ) 2 OCOCH═CHCH 3 | D-47 | |||
| —OCOO(CH 2 ) 4 OCH═CH 2 | D-48 | |||
| | D-49 | |||
| R = | | X = | —OC 4 H 9 | D-50 |
| —OC 5 H 11 | D-51 | |||
| —OC 6 H 13 | D-52 | |||
| —OC 7 H 15 | D-53 | |||
| —OC 8 H 17 | D-54 | |||
| —OCH 2 CH(CH 3 )C 4 H 9 | D-55 | |||
| —O(CH 2 ) 2 OCOCH═CH 2 | D-56 | |||
| —O(CH 2 ) 3 OCOCH═CH 2 | D-57 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-58 | |||
| —O(CH 2 ) 5 OCOCH═CH 2 | D-59 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-60 | |||
| —O(CH 2 ) 7 OCOCH═CH 2 | D-61 | |||
| —O(CH 2 ) 8 OCOCH═CH 2 | D-62 | |||
| —O(CH 2 ) 2 CH(CH 3 )OCOCH═CH 2 | D-63 | |||
| —O(CH 2 ) 3 CH(CH 3 )OCOCH═CH 2 | D-64 | |||
| —O(CH 2 CH 2 O) 2 COCH═CH 2 | D-65 | |||
| | D-66 | |||
| —O(CH 2 ) 4 OCOCH═CHCH 3 | D-67 | |||
| —O(CH 2 ) 4 OCH═CH 2 | D-68 | |||
| | D-69 | |||
| —OCOC 4 H 9 | D-70 | |||
| —OCOC 5 H 11 | D-71 | |||
| —OCOC 6 H 13 | D-72 | |||
| —OCO(CH 2 ) 2 OCOCH═CH 2 | D-73 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-74 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-75 | |||
| —OCO(CH 2 ) 5 OCOCH═CH 2 | D-76 | |||
| —OCO(CH 2 ) 6 OCOCH═CH 2 | D-77 | |||
| —OCO(CH 2 ) 7 OCOCH═CH 2 | D-78 | |||
| —OCO(CH 2 ) 2 CH(CH 3 )OCOCH═CH 2 | D-79 | |||
| | D-80 | |||
| —OCO(CH 2 ) 2 OCOCH═CHCH 3 | D-81 | |||
| —OCO(CH 2 ) 4 OCH═CH 2 | D-82 | |||
| | D-83 | |||
| —OCOOC 4 H 9 | D-84 | |||
| —OCOOC 5 H 11 | D-85 | |||
| —OCOOC 6 H 13 | D-86 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-87 | |||
| —OCOO(CH 2 ) 3 OCOCH═CH 2 | D-88 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-89 | |||
| —OCOO(CH 2 ) 5 OCOCH═CH 2 | D-90 | |||
| —OCOO(CH 2 ) 6 OCOCH═CH 2 | D-91 | |||
| —OCOO(CH 2 ) 7 OCOCH═CH 2 | D-92 | |||
| —OCOOCH(CH 3 )CH 2 CH 2 OCOCH═CH 2 | D-93 | |||
| —OCOOCH(CH 2 CH 2 O) 2 COCH═CH 2 | D-94 | |||
| | D-95 | |||
| —OCOO(CH 2 ) 2 OCOCH═CHCH 3 | D-96 | |||
| —OCOO(CH 2 ) 4 OCH═CH 2 | D-97 | |||
| | D-98 | |||
| R = | | X = | —OC 4 H 9 | D-99 |
| —OC 5 H 11 | D-100 | |||
| —OC 6 H 13 | D-101 | |||
| —OC 7 H 15 | D-102 | |||
| —OC 8 H 17 | D-103 | |||
| —OCH 2 CH(CH 3 )C 4 H 9 | D-104 | |||
| —O(CH 2 ) 2 OCOCH═CH 2 | D-105 | |||
| —O(CH 2 ) 3 OCOCH═CH 2 | D-106 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-107 | |||
| —O(CH 2 ) 5 OCOCH═CH 2 | D-108 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-109 | |||
| —O(CH 2 ) 7 OCOCH═CH 2 | D-110 | |||
| —O(CH 2 ) 8 OCOCH═CH 2 | D-111 | |||
| —O(CH 2 ) 2 CH(CH 3 )OCOCH═CH 2 | D-112 | |||
| —O(CH 2 ) 3 CH(CH 3 )OCOCH═CH 2 | D-113 | |||
| —O(CH 2 CH 2 O) 2 COCH═CH 2 | D-114 | |||
| | D-115 | |||
| —O(CH 2 ) 4 OCOCH═CHCH 3 | D-116 | |||
| —O(CH 2 ) 4 OCH═CH 2 | D-117 | |||
| | D-118 | |||
| —OCOC 4 H 9 | D-119 | |||
| —OCOC 5 H 11 | D-120 | |||
| —OCOC 6 H 13 | D-121 | |||
| —OCO(CH 2 ) 2 OCOCH═CH 2 | D-122 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-123 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-124 | |||
| —OCO(CH 2 ) 5 OCOCH═CH 2 | D-125 | |||
| —OCO(CH 2 ) 6 OCOCH═CH 2 | D-126 | |||
| —OCO(CH 2 ) 7 OCOCH═CH 2 | D-127 | |||
| —OCO(CH 2 ) 2 CH(CH 3 )OCOCH═CH 2 | D-128 | |||
| | D-129 | |||
| —OCO(CH 2 ) 2 OCOCH═CHCH 3 | D-130 | |||
| —OCO(CH 2 ) 4 OCH═CH 2 | D-131 | |||
| | D-132 | |||
| —OCOOC 4 H 9 | D-133 | |||
| —OCOOC 5 H 11 | D-134 | |||
| —OCOOC 6 H 13 | D-135 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-136 | |||
| —OCOO(CH 2 ) 3 OCOCH═CH 2 | D-137 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-138 | |||
| —OCOO(CH 2 ) 5 OCOCH═CH 2 | D-139 | |||
| —OCOO(CH 2 ) 6 OCOCH═CH 2 | D-140 | |||
| —OCOO(CH 2 ) 7 OCOCH═CH 2 | D-141 | |||
| —OCOOCH(CH 3 )CH 2 CH 2 OCOCH═CH 2 | D-142 | |||
| —OCOOCH(CH 2 CH 2 O) 2 COCH═CH 2 | D-143 | |||
| | D-144 | |||
| —OCOO(CH 2 ) 2 OCOCH═CHCH 3 | D-145 | |||
| —OCOO(CH 2 ) 4 OCH═CH 2 | D-146 | |||
| | D-147 | |||
| R = | | X = | —OC 6 H 13 | D-148 |
| —OCOC 5 H 11 | D-149 | |||
| —OCOOC 4 H 9 | D-150 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-151 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-152 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-153 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-154 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-155 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-156 | |||
| R = | | X = | —OC 6 H 13 | D-157 |
| —OCOC 5 H 11 | D-158 | |||
| —OCOOC 4 H 9 | D-159 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-160 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-161 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-162 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-163 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-164 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-165 | |||
| R = | | X = | —OC 6 H 13 | D-166 |
| —OCOC 5 H 11 | D-167 | |||
| —OCOOC 4 H 9 | D-168 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-169 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-170 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-171 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-172 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-173 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-174 | |||
| R = | | X = | —OC 6 H 13 | D-175 |
| —OCOC 5 H 11 | D-176 | |||
| —OCOOC 4 H 9 | D-178 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-179 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-180 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-181 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-182 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-183 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-184 | |||
| R = | | X = | —OC 6 H 13 | D-185 |
| —OCOC 5 H 11 | D-186 | |||
| —OCOOC 4 H 9 | D-187 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-188 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-189 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-190 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-191 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-192 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-193 | |||
| R = | | X = | —OC 6 H 13 | D-194 |
| —OCOC 5 H 11 | D-195 | |||
| —OCOOC 4 H 9 | D-196 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-197 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-198 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-199 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-200 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-201 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-202 | |||
| R = | | X = | —OC 6 H 13 | D-203 |
| —OCOC 5 H 11 | D-204 | |||
| —OCOOC 4 H 9 | D-205 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-206 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-207 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-208 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-209 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-210 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-211 | |||
| R = | | X = | —OC 6 H 13 | D-212 |
| —OCOC 5 H 11 | D-213 | |||
| —OCOOC 4 H 9 | D-214 | |||
| —O(CH 2 ) 4 OCOCH═CH 2 | D-215 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-216 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-217 | |||
| —OCO(CH 2 ) 4 OCOCH═CH 2 | D-218 | |||
| —OCOO(CH 2 ) 2 OCOCH═CH 2 | D-219 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-220 | |||
| R = | | X = | —OC 6 H 13 | D-221 |
| —OCOC 5 H 11 | D-222 | |||
| —OCOOC 4 H 9 | D-223 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-224 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-225 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-226 | |||
| R = | | X = | —OC 6 H 13 | D-227 |
| —OCOC 5 H 11 | D-228 | |||
| —OCOOC 4 H 9 | D-229 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-230 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-231 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-232 | |||
| R = | | X = | —OC 6 H 13 | D-233 |
| —OCOC 5 H 11 | D-234 | |||
| —OCOOC 4 H 9 | D-235 | |||
| —O(CH 2 ) 6 OCOCH═CH 2 | D-236 | |||
| —OCO(CH 2 ) 3 OCOCH═CH 2 | D-237 | |||
| —OCOO(CH 2 ) 4 OCOCH═CH 2 | D-238 | |||
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-239 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-240 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-241 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-242 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-243 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-244 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-245 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-246 | |
| R = | | —O(CH 2 ) 6 OCOCH═CH 2 | D-247 | |
| R = | | X = | —C 8 H 17 | D-248 |
| | D-249 | |||
| | D-250 | |||
| | D-251 | |||
| | D-252 | |||
| | D-253 | |||
| | D-254 | |||
| | D-255 | |||
| —(CH 2 ) 2 OCOCH═CH 2 | D-256 | |||
| —COO(CH 2 ) 4 OCOCH═CH 2 | D-257 | |||
| | D-258 | |||
| | D-259 | |||
| | D-260 | |||
| | D-261 | |||
| | D-262 | |||
| | D-263 | |||
| | ||||
| R = | | X = | —O(CH 2 ) 2 OCOCH═CH 2 | D-264 |
| | ||||
| R = | | —O(CH 2 ) 3 OCOCH═CH 2 | D-265 | |
| R = | | —O(CH 2 ) 4 OCOCH═CH 2 | D-266 | |
| R = | | —O(CH 2 ) 4 OCOCH═CH 2 | D-267 | |
| R = | | —O(CH 2 ) 3 OCOCH═CH 2 | D-268 | |
| R = | | —O(CH 2 ) 4 OCOCH═CH 2 | D-269 | |
| | ||||
| R = | | X = | —O(CH 2 ) 2 OCOCH═CH 2 | D-270 |
| | ||||
| R = | | —O(CH 2 ) 3 OCOCH═CH 2 | D-271 | |
| | ||||
| R = | | —O(CH 2 ) 4 OCOCH═CH 2 | D-272 | |
| | ||||
| R = | | —O(CH 2 ) 2 OCOCH═CH 2 | D-273 | |
| R = | | —O(CH 2 ) 3 OCOCH═CH 2 | D-274 | |
| R = | | —O(CH 2 ) 4 OCOCH═CH 2 | D-275 | |
| R = | | X = | —O(CH 2 ) 2 OCOCH═CH 2 —OC 6 H 13 | D-276D-277 |
| | X = | —O(CH 2 ) 2 OCOCH═CH 2 —OC 6 H 13 | D-278D-279 | |
| | X = | —O(CH 2 ) 2 OCOCH═CH 2 —OC 6 H 13 | ||