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    • 专利摘要:
    The polymerizable compound of the present invention is represented by the following general formula (101): (101) Wherein R is H, R ', R'O, R'COO or R'OCO; R 'is a straight or branched alkyl or alkenyl group having 1 to 15 carbon atoms; A 1 and A 2 are independently a cyclohexane ring or a benzene ring which may include a substituent represented by the following general formula (102); X is H or CH 3 ; And Y 1 , Y 2 , Y 3 and Y 4 are independently H, F, Cl, CH 3 , CH 3 O, CF 3 or CF 3 O, wherein Y 1 , Y 2 , Y 3 and Y 4 are At least one is H and if A 1 and A 2 are both cyclohexane rings, then at least one of Y 1 , Y 2 , Y 3 and Y 4 is not H; (102) Wherein Y 5 , Y 6 , Y 7 and Y 8 are independently H, F, Cl, CH 3 , CH 3 O, CF 3 or CF 3 O, and Y 5 , Y 6 , Y 7 and Y 8 Two or more are H.
    公开号:KR19990068186A
    申请号:KR1019990002763
    申请日:1999-01-28
    公开日:1999-08-25
    发明作者:오니시노리아키；미야자키아야；미조베호요；요시다마사히코；스즈끼켄지
    申请人:마찌다 가쯔히꼬；샤프 가부시키가이샤；노자와 순따로；간또 가가꾸 가부시끼가이샤；
    IPC主号:
    专利说明:

    Polymerizable compound, polymerizable resin composition, cured polymer and liquid crystal display device
    The present invention relates to liquid crystal displays used by individuals or many people, such as word processors, personal computers or mobile information terminals, polymerizable compounds suitable for liquid crystal displays, polymerizable resin compositions containing such compounds and cured formed from such compositions. It relates to a polymer. In the present specification, the liquid crystal display device will be simply abbreviated as "LCD device".
    The following LCD devices are commonly known which use a composite material of a liquid crystal material and a polymer.
    In Japanese Laid-Open PCT Publication No. 58-501631, for example, a polymer dispersed liquid crystal display device (hereinafter referred to as "PDLC display device") is disclosed. This PDLC display includes a liquid crystal region surrounded by a polymer matrix. If no voltage is applied to the liquid crystal material, the refractive indices of the liquid crystal material and polymer do not match, resulting in a scattering state. When a voltage is applied to the liquid crystal material, the refractive index of the liquid crystal material matches the refractive index of the polymer to cause a transparent state.
    Japanese Laid-Open PCT Publication No. 61-502128 discloses an LCD device in which three-dimensional phase separation of a liquid crystal material and a polymer is performed by irradiating ultraviolet light to a mixture of a liquid crystal material and a photopolymerizable resin, for example.
    The LCD device described above performs display by electrically controlling the liquid crystal material to be in a scattering state or in a transparent state.
    In Japanese Patent Laid-Open No. 1-269922, the following method is disclosed. The mixture of liquid crystal material and photopolymerizable resin is first exposed to ultraviolet light through a photomask. After removal of the photomask, the mixture is exposed to ultraviolet light a second time to irradiate ultraviolet light with the area masked by the photomask during the first exposure. Thus, regions having different display characteristics were formed. The LCD device manufactured by the above method basically performs the display in the scattering mode.
    Japanese Patent Laid-Open No. 5-257135 discloses an LCD device manufactured by the following method. An alignment layer having an orientation control force is provided on two substrates. A mixture of a liquid crystal material and a photopolymerizable resin is injected between the two substrates. The mixture of the liquid crystal material and the photopolymerizable resin is irradiated with ultraviolet light through a photomask. The LCD device manufactured by this method is used for the static driving in which the liquid crystal region is patterned from the outside of the cell by using the difference between the region shielded by the photomask and the region not shielded by the photomask.
    In order to improve the visual characteristics of LCD devices, it is proposed to use a composite material of a liquid crystal material and a polymer. The liquid crystal molecules need to be aligned in three or more directions in the pixel region in order to improve the alignment state and visual characteristics of the liquid crystal molecules.
    8A and 8B, the visual characteristics of the LCD device in the optical visual mode will be described.
    8A schematically shows the relationship between the change in liquid crystal orientation and visual characteristics as voltage is applied to the optical viewing mode LCD device 10. 9B schematically illustrates the relationship in a conventional twisted nematic (TN) mode LCD device. In both Figures 8A and 8B, part (a) shows a state where no voltage is applied, part (b) shows an intermediate stage in which some voltage is applied but not enough, and (c) part is a sufficient voltage. The authorized state is shown.
    As shown in Fig. 8A, the optical viewing mode LCD device 10 includes a substrate 1 and a second one. The liquid crystal layer interposed between the substrates 1, 2 comprises a polymer wall 7 surrounded by a liquid crystal region 8. The liquid crystal molecules 9 contained in the liquid crystal region 8 are symmetrically oriented with respect to the axis 6. Therefore, the apparent refractive indices of the liquid crystal molecules 9 seen in the A and B directions in the intermediate state shown in part (b) become the same on average. As a result, the visual characteristic is improved compared to the TN mode shown in Fig. 8B.
    In the conventional TN mode LCD device shown in Fig. 8B, the liquid crystal molecules have only one orientation direction in the intermediate state shown in part (b). Therefore, display characteristics such as brightness and apparent refractive index of the liquid crystal molecules viewed in the A and B directions are different. As a result, the visual characteristic becomes inferior to the visual characteristic of the LCD device 10.
    The following LCD device is disclosed as an optical viewing mode LCD device.
    Japanese Patent Laid-Open Nos. 4-338923 and 4-212928 disclose a wide-view mode LCD device manufactured by combining the above-described PDLC display device and a polarizing plate having a polarization axis orthogonal to each other.
    Japanese Patent Laid-Open No. 5-27242 discloses a method for improving the visual characteristics of a non-scattering mode LCD device using a polarizing plate. According to this method, the mixture of the liquid crystal material and the photopolymerizable resin is phase separated, and then a liquid crystal layer formed of the composite material of the liquid crystal material and the polymer is formed. By this method, the orientation of the liquid crystal region is randomized by the resulting polymer. That is, the liquid crystal molecules in different regions stand in different orientation directions when a voltage is applied. As a result, the transmittances of the liquid crystal molecules seen in the plurality of directions become the same, so that the visual characteristics can be improved to half-tone display.
    The applicant of the present invention discloses the following LCD device in Japanese Patent Laid-Open No. 6-301015. This LCD device uses a photomask or the like during photopolymerization so that liquid crystal molecules are oriented in all directions (axially symmetrical) in the pixel region and the region shielded by the photomask forms a polymer wall formed mainly of a photocurable resin. By adjusting.
    In the above-described LCD device, declining occurs at the interface between the polymer wall and the liquid crystal region due to reverse tilt of the liquid crystal molecules in the liquid crystal region. Since the disclination appears as a bright line when displayed, display characteristics in a black state are deteriorated.
    In order to solve the problem that the disclination occurs when a voltage is applied, the applicant of the present invention in Japanese Patent Laid-Open No. 7-120728 discloses a technique for adding a polymerizable compound having a liquid crystal phase structure to the mixture of the liquid crystal composition and the photocurable resin Is starting.
    However, using the above-described polymerizable compound may cause the following problems.
    First, in the normally white mode, the pretilt of the liquid crystal molecules becomes large in the liquid crystal region, thereby reducing the brightness of the display when no voltage is applied.
    Second, the response speed is deteriorated due to the interaction between the polymer and the liquid crystal material in the composite layer and the interface between the polymer wall and the liquid crystal region at its interface, or the threshold characteristics and sharpness of the voltage versus transmittance characteristic. Deteriorates.
    In an LCD device having improved visual characteristics, such as the device disclosed in Japanese Patent Laid-Open No. 6-301015, (1) the orientation of the liquid crystal molecules is controlled so that the liquid crystal molecules are oriented in all directions, and (2) at the interface of the liquid crystal material and the polymer. It is difficult to prevent the reduction of contrast caused by the depolarized light of scattered light.
    In order to suppress light scattering at the interface of the liquid crystal material and the polymer, the occurrence of the interface in the pixel region can be reduced. In order to reduce the occurrence of the interface, it is necessary to control the size and position of liquid crystal droplets made of a three-dimensional polymer matrix. However, this control is extremely difficult in the conventional method.
    In order to solve the above-mentioned problem, it is important to select the polymerizable compound appropriately so as not only to suppress the occurrence of declining but also to reduce the response speed and the voltage vs. transmittance characteristic. It would also be advantageous for more than one liquid crystal droplet to be formed in one pixel region.
    That is, in order to realize an LCD device in which the conventional liquid crystal mode is similarly solidified, the above-described problem of controlling the orientation of liquid crystal molecules and controlling the scattering intensity at the interface should preferably be solved simultaneously or at least individually. Therefore, it is very important to obtain a polymerizable compound that can solve all these problems.
    In the case of using a polymerizable compound having a liquid crystal-like structure as described above, when such a compound has a relatively high degree of polymerization, printing afterimage phenomenon is prevented by disturbing the alignment of liquid crystal molecules to provide an excessively strong memory effect at the interface between the liquid crystal material and the polymer. Triggered. Therefore, the provision of suitable polymerizable compounds is a critical task.
    1 shows a method for synthesizing a polymerizable compound according to a feature of the invention,
    2 shows a process for the synthesis of reaction intermediates for polymerizable compounds in accordance with aspects of the present invention,
    3 shows a synthesis method for a reaction intermediate for a polymerizable compound according to a feature of the present invention,
    4 shows a method for synthesizing a polymerizable compound according to a feature of the invention,
    5 shows a method for the synthesis of reaction intermediates of polymerizable compounds in accordance with aspects of the present invention,
    6A, 6B, 6C and 6D show methods for the synthesis of reaction intermediates of polymeric compounds in accordance with aspects of the present invention,
    7 shows a process for the synthesis of reaction intermediates of polymerizable compounds in accordance with aspects of the present invention,
    8A and 8B are schematic cross-sectional views of an LCD device and a conventional TN-type LCD device according to aspects of the present invention, and illustrate the relationship between the orientation change and visual characteristics of liquid crystal molecules according to voltage application;
    9 is a schematic plan view of the photomask used in Examples 1 to 3 according to a feature of the invention;
    FIG. 10 schematically shows the LCD device of Examples 1 to 3 according to a feature of the invention as measured by a polarization microscope,
    11 is a schematic plan view of a substrate of an LCD device in Embodiments 4 to 6 in accordance with a feature of the invention showing a patterning wall;
    12A is a schematic cross-sectional view of the substrate of the LCD device in Embodiments 4 to 6 according to a feature of the present invention;
    12B is a schematic plan view of the substrate shown in FIG. 12A;
    Fig. 13 is a schematic sectional view of an LCD device in Embodiment 9 in accordance with a feature of the present invention;
    The polymerizable compound of the present invention is represented by the formula (101):
    (101)
    In the food,
    R is H, R ', R'O, R'COO or R'OCO;
    R 'is a straight or branched alkyl or alkenyl group having 1 to 15 carbon atoms;
    A 1 and A 2 are independently a cyclohexane ring or a benzene ring which may include a substituent represented by the following general formula (102);
    X is H or CH 3 ; In addition
    Y 1 , Y 2 , Y 3 and Y 4 are independently H, F, Cl, CH 3 , CH 3 O, CF 3 or CF 3 O, wherein two of Y 1 , Y 2 , Y 3 and Y 4 The above is H, and when A 1 and A 2 are both cyclohexane rings, at least one of Y 1 , Y 2 , Y 3 and Y 4 is not H;
    (102)
    Wherein Y 5 , Y 6 , Y 7 and Y 8 are independently H, F, Cl, CH 3 , CH 3 O, CF 3 or CF 3 O, and Y 5 , Y 6 , Y 7 and Y 8 Two or more are H.
    One embodiment of the invention is that in formula (101) A 1 is a cyclohexane ring and A 2 is a benzene ring.
    Another embodiment of the invention is that A 1 and A 2 in formula (101) are cyclohexane rings.
    The 1st summary of this invention is providing the polymeric resin composition containing the polymeric resin material containing the polymeric compound mentioned above, and the photoinitiator mixed with each other.
    Alternatively, the polymerizable compound of the present invention is represented by the following formula (103):
    (103)
    In the food,
    R is a straight or branched chain alkyl or alkoxy group having 1 to 15 carbon atoms where H, F or any hydrogen atom may be substituted by a fluorine atom;
    Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 are independently H or F;
    X is H or CH 3 ;
    At least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 is F, provided that R is a straight chain alkyl group with no hydrogen atoms substituted by fluorine atoms.
    Another aspect of the present invention is to provide a cured polymer obtained by polymerizing the polymerizable resin composition described above.
    Another aspect of the present invention is to provide a liquid crystal display device. The liquid crystal display comprises a polymer wall and a liquid crystal region enclosed by the polymer wall, wherein the polymer wall and the liquid crystal region are interposed between the pair of substrates and the polymer wall comprises the cured polymer described above.
    One embodiment of the invention includes the polymerizable compound in an amount of from about 3% by weight to about 40% by weight.
    Alternatively, the liquid crystal display of the present invention includes a polymer wall and a liquid crystal region surrounded by the polymer wall, wherein the polymer wall and the liquid crystal region are interposed between the pair of substrates and at least a portion of the polymer wall in contact with the liquid crystal region. The region includes the cured polymer described above.
    In one embodiment of the present invention, the liquid crystal molecules in the liquid crystal region are oriented in the axisymmetric state.
    In another embodiment of the present invention, the liquid crystal regions are regularly aligned.
    In another embodiment of the present invention, the liquid crystal display further comprises a liquid crystal alignment layer provided on at least one surface of the pair of substrates, the surface of which is in contact with the liquid crystal region.
    In another embodiment of the present invention, the liquid crystal molecules in the liquid crystal region are oriented in any of the twisted nematic type, the super twisted nematic type and the surface stabilized ferroelectric liquid crystal type.
    In another embodiment of the present invention, the liquid crystal regions are each provided in one pixel region which is the minimum unit for display.
    Any hydrogen means one or more hydrogen atoms on an alkyl or alkoxy group substituted by a fluorine atom.
    Accordingly, the polymerizable compound according to the present invention is a compound having a liquid crystal like structure and a polymerizable functional group in the molecule. The presence of a liquid crystal like structure in the molecule stabilizes the orientation of the liquid crystal molecules in the liquid crystal region. The polymerizable functional group is a styrene or methylstyrene group having excellent selectivity and high polymerization rate during the polymerization reaction. This reduces the anchoring strength of the liquid crystal molecules by adjusting the interaction at the polymer interface with the liquid crystal molecules.
    Therefore, the present invention described herein can (1) minimize the reduction of response speed and voltage-to-transmittance characteristics without disturbing the alignment state of the liquid crystal molecules, and have an improved contrast ratio and suppress the occurrence of afterimage printing even in a fixed display. Which can provide a liquid crystal display device which can be used, (2) a polymerizable compound suitable for the above-mentioned liquid crystal display device, (3) a polymerizable resin composition containing such a compound, and (4) a cured polymer formed from such a composition. .
    The above and other advantages of the present invention will be apparent to those of ordinary skill in the art having read and understood the following detailed description with reference to the accompanying drawings.
    Hereinafter, the present invention will be described in detail with reference to Examples. As used herein, a liquid crystal layer having "a liquid crystal region surrounded by a polymer wall or molecular structure" has a liquid crystal region in which liquid crystal molecules in the liquid crystal layer are separated from other liquid crystal molecules by the presence of a polymer, so that the liquid crystal region is completely surrounded by a polymer wall. A structure for forming a plurality of liquid crystal regions, including a liquid crystal layer having a liquid crystal region partitioned by a layer, columnar or wall polymer, and a liquid crystal layer having a liquid crystal region segmented by a three-dimensional network structure composed of a polymer. It refers to the liquid crystal layer having.
    (Polymerizable compound)
    [rescue]
    The polymerizable compound according to the present invention is a compound having a structure similar to that of the liquid crystal compound and a single functional structure having a polymerizable functional group bonded to this metogen group and having one polymerizable group in a molecule. One of the most important features of the polymerizable compound of the present invention is that the polymerizable functional group is a styrene or methylstyrene group represented by the above formula (101) or (103).
    [Characteristics of styrene and methyl styrene polymerizable compounds]
    Styrene resins are generally characterized as having a low polymerization reactivity compared to acrylate resins and methacrylate resins. More specifically, the free radicals in the reaction intermediate of the styrene functional group in the optical radical polymerization reaction are more stabilized and have a longer lifetime because of the lower polymerization reactivity due to the non-coordination effect of electrons than the acrylate functional group. When the polymerization reactivity is low, there is a tendency to improve the selectivity of the polymerization reaction containing a styrene compound. As a result, the polymerization conversion rate may be improved, and thus more uniform polymerization may be performed.
    The above characteristics are more pronounced when the double bond carbon is methylated because the free radicals of the reaction intermediate are more stabilized.
    The above-mentioned problems of the prior art can be minimized or effectively solved by adding at least one styrene or methylstyrene polymerizable compound having the above-described characteristics to the polymerizable resin at a predetermined ratio.
    By using the polymerizable compound according to the present invention, the following effects can be obtained.
    1) When using a mixture of a liquid crystal material and a polymerizable resin for an LCD device of a display mode using the alignment regulating force of an alignment film provided on a substrate, a polymer layer formed of a composite of a polymer and a liquid crystal material is formed between the alignment film and the liquid crystal region. do. This generally tends to reduce the alignment regulating force of the alignment film on the liquid crystal molecules in the liquid crystal region.
    When the polymerizable compound having a liquid crystal like structure according to the present invention is included in the polymerized layer, the polymerizable compound may express the alignment regulating force of the alignment film on the liquid crystal molecules in the liquid crystal region to stabilize the alignment state of the liquid crystal molecules.
    2) When the liquid crystal display molecules present in the liquid crystal region are oriented in the axisymmetric state, a disclination line usually occurs due to the reverse tilt of the liquid crystal molecules along the periphery of the liquid crystal region when a voltage is applied.
    By using the polymerization compound according to the present invention, the liquid crystal molecules are provided with pretilt on the surface of the substrate. This suppresses the occurrence of the disclination line.
    3) The two effects mentioned above can be obtained from the polymerizable compound proposed in Japanese Patent Laid-Open No. 7-120728, which is incorporated herein by reference. However, as mentioned above, conventional polymerizable compounds have problems caused by a decrease in response speed due to interactions at the liquid crystal region and the polymer wall interface, a threshold characteristic in voltage vs. transmittance characteristics, and a decrease in sharpness. Therefore, conventional polymerizable compounds still have problems to be solved in terms of electro-optical properties.
    The polymerizable compound having a styrene or methylstyrene functional group according to the present invention can adjust the interaction at the interface of the liquid crystal and the polymer wall, thereby reducing the angling strength of the liquid crystal molecules. By using such a polymerizable compound, printing afterimage caused by excessively strong memory effect at the interface can be suppressed, as well as problems caused by a decrease in response speed, a threshold characteristic in voltage versus transmittance characteristics and a decrease in sharpness. have.
    When A 1 in the formula (101) is a cyclohexane ring and A 2 is a benzine ring, the selectivity of the polymerization reaction can be easily improved.
    If both A 1 and A 2 in the formula (101) are cyclohexane rings, the refractive index of the produced polymer is small. This makes it easy to match the refractive index between the polymer and the liquid crystal material, so that high contrast display can be obtained.
    When a fluorine atom is introduced into the portion of the liquid crystal like core structure, the alignment state of the liquid crystal molecules in the liquid crystal region can be further stabilized. More specifically, the fluorine atoms on the surface of the polymer wall itself can be easily oriented by fluorinating the metogen groups. This reduces the surface energy of the polymer wall, reducing the anchoring strength of the liquid crystal molecules. In this way the memory effect can be adjusted.
    (Synthesis method)
    The polymerizable compound according to the present invention can be synthesized in the following manner. The synthetic methods described below are merely exemplary and are not intended to limit the invention.
    [Synthesis of polymeric compound represented by formula (101)]
    The polymerizable compound represented by the formula (101) may be obtained via the reaction intermediate (1) according to the synthesis method shown in FIG.
    1) When Z = COCH 3
    If X is H, the reaction intermediate (1) is reduced using sodium borohydride to produce the reaction intermediate (2). If X = CH 3 , the reaction intermediate (1) is reacted with methylmagnesium bromide to produce the reaction intermediate (2).
    The reaction intermediate (2) is dehydrated with toluenesulfonic acid to give the desired polymerizable compound (1) according to the invention.
    2) Z = Br, I, OSO 2 CF 3
    If X is H, the reaction intermediate 1 reacts with tributylvinyltin in the presence of a palladium catalyst to produce the polymerizable compound 101 according to the present invention. If X = CH 3 , the reaction intermediate 1 reacts with tributyl (1-methylvinyl) tin to produce the polymerizable compound 101 according to the present invention.
    3) Z = CHO
    If X is H, the reaction intermediate (1) reacts with Wittig with methyl triphenylphosphonium iodide to give the desired polymerizable compound (101) according to the invention.
    The reaction intermediate (1) can be synthesized according to the synthesis method shown in Figs. 2 and 3, for example.
    2 shows a method for synthesizing the reaction intermediate (1) in which R is H or R ', A 1 is a cyclohexane ring, and A 2 is a benzene ring.
    (2-1) Trans-alkylcyclohexylphenylboric acid (3) and bromoiodobenzene compound (4) are coupled in the presence of a palladium catalyst to produce a reaction intermediate (1).
    As the bromoodobenzene compound (4), a compound represented by the following structural formula is commercially available:
    (2-2) Trans-alkylcyclohexylphenylboric acid (3) and bromobenzene compound (5) are coupled in the presence of a palladium catalyst to produce compound (6), which in turn is in combination with dimethylformaldehyde in the presence of butyllithium. By reaction to produce reaction intermediate (1).
    As the bromobenzene compound (5), the compound represented by the following structural formula is marketed.
    (2-3) Trans-alkylcyclohexylphenylboric acid (3) and bromonitrobenzene compound (7) are coupled in the presence of a palladium catalyst to produce compound (9). The nitro group of compound (9) is reduced to give compound (10), which in turn is Sandmeyer reacted to produce reaction intermediate (1).
    Compound (10) can also be obtained by direct coupling reaction between alkylcyclohexylphenyl boric acid (3) and bromoaniline compound (8).
    As the bromonitrobenzene compound (7), a compound represented by the following structural formula is commercially available:
    As the bromoaniline compound (8), a compound represented by the following structural formula is commercially available:
    (2-4) Trans-alkylcyclohexylphenylboric acid (3) and bromophenol compound (11) were coupled in the presence of a palladium catalyst to obtain compound (12), which was then reacted with trifluoromethanesulfonic anhydride to react Intermediate (1) is obtained.
    The hydroxyl group of the bromophenol compound (11) may be previously protected with a protecting group. After coupling, the protecting group can be removed.
    As the bromophenol compound (11), a compound represented by the following structural formula is commercially available:
    FIG. 3 shows a process for the synthesis of reaction intermediate (1) in which R = H or R 'and A 1 and A 2 are both cyclohexane rings.
    (3-1) Compound (13) and bromoiodobenzene compound (4) are condensed in the presence of butyllithium to obtain compound (14), which is then dehydrated using toluenesulfonic acid to obtain compound (15). The reaction intermediate (1) is then obtained by hydrogenating compound (15) in the presence of a platinum oxide catalyst and isolating the trans form of compound (15) by recrystallization or column chromatography.
    (3-2) Compound (13) and bromobenzene compound (5) are condensed in the presence of butyllithium to obtain compound (16), which is then hydrogenated with toluenesulfonic acid to give compound (17). Thereafter, compound (17) is hydrogenated in the presence of a Pd-C catalyst and compound (18) is obtained by isolating the trans form of compound (17) by recrystallization or column chromatography. Compound (18) is then reacted with dimethylformaldehyde in the presence of butyllithium to obtain reaction intermediate (1).
    (3-3) Compound (13) and bromonitrobenzene compound (7) are condensed in the presence of butyllithium to obtain compound (19), which is then dehydrated using toluenesulfonic acid to obtain compound (20). Thereafter, compound 20 is hydrogenated in the presence of a Pd-C catalyst or a platinum oxide catalyst and the trans form is isolated by recrystallization or column chromatography to obtain compound 21. Sandmeyer reaction of compound (21) gives reaction intermediate (1).
    (3-4) The hydroxyl group of the bromophenol compound (11) is protected with a methoxymethyl group to give the compound (22). Compounds (13) and (22) are condensed in the presence of butyllithium to afford compound (23), which is again dehydrated using toluenesulfonic acid. Removal of the protecting group yields compound (24). Thereafter, compound 24 is hydrogenated in the presence of a Pd-C catalyst or a platinum oxide catalyst and the trans form is isolated by recrystallization or column chromatography to obtain compound 25. This compound (25) is again reacted with trifluoromethanesulfonic anhydride to obtain reaction intermediate (1).
    Reaction intermediates other than the reaction intermediate 1 shown in FIGS. 2 and 3 can be synthesized by selecting a suitable material and carrying out reactions such as oxidation, reduction, substitution of functional groups, and coupling.
    [Synthesis of polymeric compound represented by the formula (103)]
    The polymerizable compound represented by the formula (103) can be obtained via the reaction intermediate 31, for example, according to the synthesis method shown in FIG.
    1) When Z = COCH 3
    If X is H, the reaction intermediate 31 is reduced by sodium borohydride to obtain the reaction intermediate 32. If X = CH 3 , the reaction intermediate 31 reacts with methylmagnesium bromide to produce the reaction intermediate 32.
    This reaction intermediate 32 is dehydrated using toluenesulfonic acid to give the desired polymerizable compound 103 according to the invention.
    2) Z = Br, I, OSO 2 CF 3
    If X is H, the reaction intermediate 31 is reacted with tributylvinyltin in the presence of a palladium catalyst to give the desired polymerizable compound 3 according to the invention. If X = CH 3 , the reaction intermediate 31 is reacted with tributyl (1-methylvinyl) tin to give the desired polymerizable compound 103 according to the invention.
    3) Z = CHO
    If X = H, the reaction intermediate (31) is reacted with the methyltriphenylphosphonium iodide by bite to obtain the desired polymerizable compound (103) according to the present invention.
    This reaction intermediate 31 can be synthesized according to the synthesis method shown for example in FIGS. 5 and 6.
    (5-1) when R is an alkyl group
    Compound (33) is coupled with alkylmagnesium bromide (RMgBr) in the presence of a palladium catalyst to give compound (34). If R is a perfluoroalkyl group, compound (33) is coupled with the iodide perfluoroalkyl in the presence of a copper catalyst to give compound (34). Trimethyl borate is then added to compound (34) to hydrolyze compound (34) under acidic conditions to yield compound (35).
    The reaction intermediate 31 is obtained using compound 34 or 35 according to the method shown in FIGS. 6A-6D as follows.
    (a) Compound (39) is hydrolyzed by reacting Compound (39) with trimethyl borate in the presence of butyllithium to afford Compound (40).
    Compound (34, 40) or compound (35, 39) is coupled in the presence of a palladium catalyst to obtain reaction intermediate 31.
    As the compounds (33) and (39), compounds represented by the following structural formulas are commercially available:
    (b) The hydroxyl group of compound (41) is protected with a benzyl group to yield compound (42). Compound 42 is coupled with compound 35 in the presence of a palladium catalyst to yield compound 47. The protecting group is removed with Pd-C and hydrogen gas to give compound 48, which reacts with trifluoromethanesulfonic anhydride to produce reaction intermediate 31.
    As the compound (41), a compound represented by the following structural formula is commercially available:
    (c) Compound (35) and Compound (49) are coupled in the presence of a palladium catalyst to yield Compound (50). The nitro group of compound 50 is reduced using Pd-C and hydrogen gas to produce compound 51, which is then sandmer-reacted to produce reaction intermediate 31.
    As the compound (49), a compound represented by the following structural formula is commercially available:
    (d) Compound (35) and Compound (52) are coupled in the presence of a palladium catalyst to give Compound (53). Trimethyl borate is added to compound (53) in the presence of butyllithium to give compound (54) by hydrolysis under acidic conditions. This compound (54) is oxidized with hydrogen peroxide to give a compound (55), which is reacted with trifluoromethanesulfonic anhydride to obtain a reaction intermediate (31).
    As the compound (52), a compound represented by the following structural formula is commercially available:
    (5-2) R = alkoxy group
    Compound (36) is etherified using alkyl bromide (R'Br), alkyl tosylate (R'OTs), alkyl triflate (R'OTf) and the like to give compound (37). Trimethyl borate is added to compound (37) in the presence of butyllithium to compound (37) to hydrolyze under acidic conditions to give compound (38).
    Using the compound (37) instead of the compound (34) or using the compound (38) instead of the compound (35), the same operation as in the case where R described above is an alkyl group is carried out to obtain the reaction intermediate (31).
    As the compound (36), a compound represented by the following structural formula is commercially available:
    (5-3) when R = F
    Boric acid trimethyl ester is added to compound 43 in the presence of butyllithium to hydrolyze compound 43 under acidic conditions to yield compound 44.
    Using compound (43) instead of compound (34) or using compound (44) instead of compound (35), the same operation as in the case where R is an alkyl group is carried out to obtain reaction intermediate (31).
    As the compound (43), a compound represented by the following structural formula is commercially available:
    (5-4) when R = H
    Boric acid trimethyl ester is added to compound (45) in the presence of butyllithium to hydrolyze compound (45) under acidic conditions to give compound (46).
    Using compound (45) instead of compound (34) or using compound (46) instead of compound (35), the same operation as in the case where R is an alkyl group is carried out to obtain reaction intermediate (31).
    As the compound (45), a compound represented by the following structural formula is commercially available:
    When Y 1 = Y 2 = Y 3 = Y 4 = Y 5 = Y 6 = Y 7 = Y 8 = H, the reaction intermediate 31 can be synthesized according to the synthesis method shown in FIG. 7 described below. have.
    (6-1) R = alkyl group
    The hydroxy group of compound (56) is protected with a benzyl group to give compound (57). Compound (57) is coupled with alkylmagnesium bromide (RMgBr) in the presence of a palladium catalyst to give compound (58). If R is a perfluoroalkyl group, compound (57) is coupled with perfluoroalkyl iodide in the presence of a copper catalyst to give compound (58).
    The protecting group is then removed using Pd-C and hydrogen gas to give compound 59, which is reacted with trifluoromethanesulfonic anhydride to obtain reaction intermediate 31.
    (6-2) R = alkoxy group
    Compound (60) is etherified using alkyl bromide (R'Br), alkyl tosylate (R'OTs), alkyl triflate (R'OTf) and the like to give compound (61). This compound (61) is reacted with trifluoromethanesulfonic anhydride to obtain a reaction intermediate (31).
    (6-3) when R = H
    Compound 62 is reacted with trifluoromethanesulfonic anhydride to obtain reaction intermediate 31.
    (Polymeric resin composition)
    The polymerizable resin composition according to the present invention comprises a polymerizable resin material and a photoinitiator containing at least one type of polymerizable compound according to the present invention.
    [Polymeric resin material]
    The selection of the photopolymerizable resin material is important because the photopolymerizable resin material is mixed with the liquid crystal material to form a wall supporting the pair of substrates and the liquid crystal region.
    According to the present invention, the polymerizable resin material having a polymerizable functional group is preferably about 3% by weight or more and about 40% by weight or less, more preferably, in order to form a liquid crystal layer surrounded by the polymer walls described below. Preferably at least about 5% and at most about 35% by weight of the polymerizable compound according to the invention.
    If the amount of the polymerizable compound according to the present invention is less than about 3% by weight, the above effect cannot be sufficiently exhibited. When the amount exceeds about 40% by weight, the degree of polymerization of the polymerizable resin material is greatly reduced and cannot be effectively polymerized. As a result, the effect of the polymerizable resin material for stabilizing liquid crystal molecules in the liquid crystal region cannot be sufficiently achieved.
    Other usable materials having polymerizable functional groups contained in the polymerizable resin material include, for example, photocurable resin monomers. Photocurable resin monomers include, for example, acrylic acid or acrylates having C 3 or more long-chain alkyl groups or aromatic groups. Photocurable resin monomers are also isobutyl acrylate, stearyl acrylate, lauryl acrylate, isoamyl acrylate, n-butyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, 2-ethyl Hexyl acrylate, n-stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and 2-phenoxyethyl methacrylate.
    In order to improve the physical strength of the polymer, polyfunctional resins having two or more functionalities, such as those listed below, can be used: bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol methacryl Rate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate and tetramethylolmethane tetraacrylate.
    Resin prepared by halogenation, in particular chlorination or fluorination, of the abovementioned monomers can also be used. Such resins include, for example, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,4,4,4-hexachlorobutyl methacrylate, 2,2,3,3 Tetrafluoropropyl methacrylate, 2,2,3,3-tetrachloropropyl methacrylate, perfluorooctylethyl methacrylate, perchlorooctylethyl methacrylate, perfluorooctylethyl acrylate and per Chlorooctylethyl acrylate.
    The photopolymerizable resin material mentioned above can be used independently or in combination of 2 or more. The monomers described above may be mixed with chlorinated or fluorinated polymers or oligomers as needed.
    [Photo Initiator]
    As the photoinitiator, general photopolymerization initiators such as Irgacure 651, 184, 907 and Darocure 1173, 1116, 2956 can be used. A sensitizer that can be polymerized by visible light may be used to improve the retention of the photoinitiator.
    (Cured polymer)
    A mixture of the polymerizable resin composition and the liquid crystal material according to the present invention is injected into a panel and irradiated with light to obtain a liquid crystal layer in which the liquid crystal region is surrounded by the polymer wall.
    In particular, the polymerizable compound according to the present invention contains a structure similar to that of the liquid crystal molecules in the molecule. It has been found that the cured polymer obtained by the polymerization method is very effective because the region of the cured polymer in direct contact with the liquid crystal material is involved in improving the orientation stability and chemical stability of the liquid crystal molecules.
    The above-mentioned mixture can be used as the panel sealing resin used during the manufacture of the liquid crystal panel or after the liquid crystal material is injected.
    (Liquid crystal area)
    [Liquid crystal material]
    The liquid crystal materials that can be used are organic mixtures exhibiting liquid crystal states near room temperature, such as nematic liquid crystal materials (including two-frequency driving liquid crystals and liquid crystals having Δ ε <0), cholesteric liquid crystal materials (especially for visible light). Liquid crystal materials having reflective characteristics), smectic liquid crystal materials, ferroelectric liquid crystal materials (SmC * ) and discotic liquid crystal materials. These liquid crystal materials may be mixed with each other. In particular, the nematic liquid crystal material mixed with the nematic liquid crystal material or the cholesteric liquid crystal material is preferable. Since the treatment of the liquid crystal material involves a photopolymerization reaction, a liquid crystal material having sufficient resistance to chemical reactions is more preferable.
    [Orientation of Liquid Crystal Material]
    In the liquid crystal region, the liquid crystal molecules are oriented in either manner of twisted nematic (TN) type, super-twisted nematic (STN) type, electrically controlled birefringence (ECB) type or surface stabilized ferroelectric liquid crystal (SSFLC) type. Can be. Liquid crystal molecules can also be oriented in an axisymmetric manner, such as concentric, spiral or radial.
    (Manufacturing Method of Liquid Crystal Layer)
    The inventor of the present invention has studied a method of arranging liquid crystal droplets having a size substantially the same as the size of one pixel so that one droplet is substantially disposed in one pixel. As a result, the following method was found to be effective.
    1) UV light is irradiated to the liquid crystal layer by shielding the area corresponding to most of the pixels by using ultraviolet light having regular ultraviolet irradiation defect sites having a size similar to the diameter of the liquid crystal droplet which is almost the same as the size of the pixel. In this way, an LCD device having a liquid crystal region surrounded by a polymer wall or wall structure can be manufactured.
    2) A material having different free energies at the interface to the liquid crystal phase and the isotropic phase is previously formed and patterned on the substrate. A liquid crystal phase is provided on this patterned material to pattern and control the free energy of the material. In this way it is possible to provide an LCD device having a liquid crystal region surrounded by a polymer wall or wall structure.
    (Retardation: d- △ n)
    In the LCD device according to the present invention having the polarizing plate, the visual characteristics are inferior when viewed in the 45 ° direction from the polarization axis of the polarizing plate. This is because (1) the polarizing plate has visual characteristics and (2) the liquid crystal layer has retardation d · Δn.
    The above-mentioned reason (2) is explained in more detail below. Light incident on the liquid crystal layer along the polarization axis of the polarizing plate includes only normal light or abnormal light when crossing the refractive index ellipsoid of the liquid crystal layer. On the other hand, light incident on the liquid crystal layer in the direction of 45 DEG from the polarization axis of the polarizing plate includes both the normal light and the abnormal light components when crossing the refractive index ellipsoid of the liquid crystal layer. For this reason, the polarization axes of two polarizing plates perpendicular to each other are apparently parallel to each other. Therefore, the light becomes elliptical polarization and light leakage becomes remarkable.
    In order to solve the above-mentioned problem, in order to suppress generation | occurrence | production of elliptically polarized light, it is preferable to make retardation of a liquid crystal layer as small as possible.
    However, when no voltage is applied, the light transmittance of the (T 0 ) liquid crystal layer is affected by retardation. Therefore, the retardation of the liquid crystal layer is preferably in the range of about 300 nm to about 650 nm to secure the omnidirectional of the visual characteristics and the brightness of the display. If the retardation is less than about 300 nm, brightness is not secured in the white display, resulting in black display. If the retardation exceeds about 650 nm, gray scale inversion of the visual characteristic occurs, causing the panel's viewing angle to be particularly narrow.
    Preferably, the twist angle of the liquid crystal molecules is about 45 to about 150 degrees. In particular, an angle of about 90 DEG near the first minimum condition is preferable in that it provides the brightest display.
    (Drive method)
    The LCD device according to the present invention has a simple matrix driving, active using switching elements such as a-Si (amorphous silicon) TFTs (thin film transistors), p-Si (polycrystalline silicon) TFTs or MIM (metal-insulator-metal elements). It may be driven by various methods such as matrix driving or plasma address driving.
    (Substrate material)
    Substrates that can be used in the present invention include glass substrates which are transparent solids and plastic substrates made of polyester films. Si substrates and opaque solid materials such as substrates coated with a thin metal film can also be used.
    Substrates coated with a thin metal film are effective for reflective LCD devices.
    Plastic substrates are preferably made of materials that do not absorb visible light, such as PET, acrylic polymers, styrene and polycarbonate. Alternatively, the plastic substrate itself may be provided with polarization power.
    Laminated substrates composed of two different types of plates may also be used. Laminated substrates consisting of two plates of the same type or of different type and of different thickness may also be used.
    Hereinafter, the present invention will be described with reference to the accompanying drawings, but the present invention is not limited thereto. The symbol used in the description of the following examples shall have the following meaning.
    GC: Gas Chromatography
    HPLC: High Performance Liquid Chromatography
    TLC: Thin Film Chromatography
    IR: infrared absorption spectrum
    Mass: mass spectrum
    b.p: boiling point
    m.p: melting point
    Y: yield
    Synthesis Example 1 Synthesis of Polymerizable Compound 4- (Trans-4 -pentylcyclohexyl) -4′-vinylbiphenyl Represented by the Following Formula (201)
    (1-a) Synthesis of Compound 4-acetyl-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by the following structural formula:
    First, 23.6 g of anhydrous aluminum chloride and 120 ml of methylene chloride were placed in a 300 ml flask. 14.0 g of acetyl chloride was added dropwise to the mixture at 5 占 폚 or lower, and the resulting mixture was stirred while maintaining at the same temperature for 30 minutes. Then, 45.2 g of 4- (trans-4-pentylcyclohexyl) biphenyl was added to the resulting mixture at 5 ° C. or lower and stirred at room temperature for 30 minutes. After the reaction, the reaction solution was poured into dilute hydrochloric acid and the organic layer was separated. The organic layer was washed with water and dried over sodium sulfate. The solvent was distilled off. The residue was recrystallized from acetone to give 24.0 g (yield: 46.0%) of 4-acetyl-4 '-(trans-4-pentylcyclohexyl) biphenyl. The purity of the resulting compound was 99.7% as measured by GC.
    (1-b) Synthesis of compound 4- (1-hydroxyethyl) -4 '-(trans-4-pentylcyclohexyl) biphenyl represented by the following structural formula
    First, 1.09 g of lithium aluminum hydride and 50 ml of anhydrous tetrahydrofuran were charged to an argon substituted 200 ml flask. Subsequently, 50 ml of anhydrous tetrahydrofuran containing 10.0 g of 4-acetyl-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from the above (1-a) synthesis was added dropwise to the resulting mixture with stirring. It was. After the dropwise addition, the resulting mixture was stirred at reflux for 2 hours. After the reaction, ethyl acetate and then 2N hydrochloric acid were added to acidify the reaction solution to deactivate unreacted lithium aluminum hydride. Ether was added to the reaction solution to separate the ether layer. The ether layer was washed with water and dried over sodium sulfate. The solvent was distilled off. The residue was recrystallized from acetone to yield 9.42 g (Y: 97.3%) of 4- (1-hydroxyethyl) -4 '-(trans-4-pentylcyclohexyl) biphenyl. The purity of the resulting mixture was 99.8% as determined by HPLC.
    (1-c) Synthesis of 4- (trans-4-pentylcyclohexyl) -4'-vinylbiphenyl represented by Chemical Formula (201)
    First, 9.39 g of 4- (1-hydroxyethyl) -4 '-(trans-4-pentylcyclohexyl) biphenyl, 0.52 g of potassium hydrogen sulfate and 50 ml of toluene were placed in a 300 ml flask equipped with a water metering tube. Charged and then azeotropically dehydrated for 4 hours at reflux. After the reaction, ether was added to the reaction solution, which was then washed with saturated brine and dried over sodium sulfate. The solvent was distilled off. The residue was recrystallized from hexane to give 1.88 g (Y: 21.1%) of 4- (trans-4-pentylcyclohexyl) vinylbiphenyl. The purity of the resulting compound was 100.0% when measured by GC, 99.9% by HPLC, and 1 spot by TLC. The phase transition temperature of the resulting compound was as follows.
    74.2 ℃ 140 ℃
    Crystals ------- → Smectic X-Phase ---- → Polymerization
    From IR measurements and mass spectral analysis, it was confirmed that the molecular ion peak is identified at 332 and that the resulting material is a compound represented by the structural formula (201) in consideration of the material used.
    Synthesis Example 2 Synthesis of Polymerizable Compound 4- (Trans-4-pentylcyclohexyl) -4 ′-(1-methylvinyl) biphenyl represented by the following Formula (202) :
    First, 0.38 g of magnesium and 1 ml of anhydrous ether were placed in an argon-substituted 50 ml flask and 0.2 g of methyl iodide was added to activate magnesium. Thereafter, 10 ml of anhydrous ether in which 1.92 g of methyl iodide was dissolved was added dropwise with stirring to the mixture. After the dropwise addition, the obtained mixture was stirred at room temperature for 1 hour. Thereafter, 40 ml of anhydrous tetrahydrofuran in which 4.18 g of 4-acetyl-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from Synthesis (1-a) was dissolved was added dropwise with stirring to the obtained mixture. And stirred at reflux for 1 h. After the reaction, 3N hydrochloric acid was added to acidify the reaction solution, ether was added to form an ether layer, and the ether layer was separated. The ether layer was washed with saturated brine and dried over sodium sulfate. Thereafter, the solvent was distilled off.
    The residue, 0.25 g potassium hydrogen sulfate, 0.15 g 4-methoxyphenol and 100 ml toluene were then placed in a 200 ml flask equipped with a water metering tube and subjected to azeotropic dehydration for 2 hours under reflux. After the reaction, the reaction solution was washed with saturated brine and dried over sodium sulfate. Thereafter, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from acetone to yield 1.63 g (Y: 39.2%) of 4- (trans-4-pentylcyclohexyl) -4 '-(1-methylvinyl) ratio. Phenyl was obtained. The purity of the obtained compound was 100.0% in GC, 99.8% in HPLC, and 1 spot in TLC. The phase transition temperature of the obtained compound is as follows:
    89.2 ℃ 186.0 ℃
    Crystal ---> Smectic B Phase ---> Smectic A Phase
    192.2 ℃ 196.8 ℃
    ---> Nematic Award ---> Isotropic
    From the IR measurement and mass spectrometry, a molecular ion peak was identified at 346, and the resultant material was found to be a compound of formula (202) in view of the raw material used.
    Synthesis Example 3 Synthesis of Polymerizable Compound 2,3-Difluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Chemical Formula (203):
    (3-a) Chemical formula Synthesis of compound 2,3-difluorophenylboronic acid represented by:
    First, 100 g of 1,2-difluorobenzene and 350 ml of anhydrous tetrahydrofuran were placed in an argon-substituted 2 L flask and cooled to -60 ° C. Thereafter, 700 ml of a hexane solution containing n-butyllithium at a concentration of 1.6 mol / l was added dropwise to the mixture obtained with stirring for 2 hours, and further stirred for 2 hours while maintaining the same temperature. Thereafter, 175 g of trimethyl borate was added dropwise and stirred for 1 hour while maintaining the same temperature. The resulting mixture was slowly cooled to room temperature, stirred for 8 hours, and then cooled to 0 ° C. The resulting reaction solution was poured into dilute hydrochloric acid to acidify the reaction solution. Thereafter, toluene was added, and the resultant toluene layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The crystallized residue was washed by dipping in a heated hexane solution to give 80.8 g of 2,3-difluorophenylboronic acid. The purity of the resulting compound was 99.5% in HPLC.
    (3-b) chemical formula Synthesis of compound 2,3-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 500 ml of benzene in which 144.6 g of 1-bromo-4- (trans-4-pentylcyclohexyl) benzene was dissolved, 78 g of 2,3-difluorophenyl boronic acid obtained from the above synthesis (3-a) 400 ml of ethanol, 500 mol of sodium carbonate solution of 2.0 mol / l and 15 g of tetrakis (triphenylphosphine) palladium (0) were placed in an argon-substituted 3 l flask and stirred under reflux for 6 hours. After the reaction, water and toluene were added to the reaction solution to perform extraction. The resulting organic layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) to give 109 g (Y: 69.9%) of 2,3-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl. The purity of the resulting compound was 98.0% by HPLC.
    (3-c) chemical formula Synthesis of compound 2,3-difluoro-4-formyl-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 300 ml of argon-substituted 24.2 g of 2,3-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl and 100 ml of anhydrous tetrahydrofuran obtained from the above synthesis (3-b) Put into flask. The resulting reaction mixture was cooled to -60 ° C. Thereafter, 60 ml of a hexane solution containing n-butyllithium at a concentration of 1.6 mol / l was added dropwise to the reaction solution with stirring for 2 hours, and further stirred for 3 hours while maintaining the same temperature. Thereafter, 20 ml of anhydrous tetrahydrofuran in which 6.2 g of dimethylformaldehyde was dissolved was added dropwise while stirring at the same temperature. The resulting reaction solution was slowly cooled to room temperature and stirred for 8 hours. After the reaction, the resulting reaction solution was poured into dilute hydrochloric acid to acidify the reaction solution. Toluene was added to the obtained solution and extraction was performed. The resulting toluene layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was recrystallized from hexane to give 13.4 g (Y: 58.4%) of 2,3-difluoro-4-formyl-4 '-(trans-4-pentylcyclohexyl) biphenyl. The purity of the resulting compound was 99.9% in HPLC.
    (3-d) Synthesis of Compound 2,3-Difluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by Formula (203):
    First, 3.71 g of t-butoxy potassium, 13.36 g of methyltriphenylphosphonium and 100 ml of anhydrous tetrahydrofuran were placed in an argon-substituted 200 ml flask and stirred under cooling for 30 minutes. Then, 50 ml of anhydrous tetrahydro containing 9.0 g of 2,3-difluoro-4-formyl-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained in Synthesis (3-c) was dissolved. Furan was added dropwise with stirring to the resulting mixture while maintaining the same temperature. After dropwise addition, water and ether were added for extraction, and the resulting ether layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) to give 0.67 g (Y: 7.5%) of 2,3-difluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl Got. The purity of the resultant compound was 100.0% in GC, 99.5% in HPLC, and 1 spot in TLC. The phase transition temperatures of the resulting compounds are as follows:
    36.0 ℃ 92.1 ℃
    Crystal ---> Smectic A Award ---> Nematic Award
    124.9 ℃
    ---> Polymerization
    From the IR measurement and mass spectrometry, a molecular ion peak was identified at 368, and the resultant material was found to be a compound of formula (203) in view of the raw material used.
    Synthesis Example 4 Synthesis of Polymerizable Compound 2-Fluoro-4 ′-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Formula (204):
    (4-a) Chemical formula Synthesis of compound 4-bromo-2-fluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 150 ml of ethanol in which 17.84 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid was dissolved, 150 ml of benzene in which 15.0 g of 4-bromo-2-fluoro-1-iodobenzene was dissolved, 49.8 ml of sodium carbonate aqueous solution and 1.44 g of tetrakis (triphenylphosphine) palladium (0) at a concentration of 2.0 mol / l were placed in an argon-substituted 500 ml flask and stirred for 37 hours under reflux. After the reaction, water and ether were added to the reaction solution to perform extraction. The resulting ether layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to give 13.6 g (Y: 67.8%) of 4-bromo-2-fluoro-4 '-(trans-4-pentylcyclohexyl). Biphenyl was obtained. The purity of the obtained compound was 99.5% in GC.
    (4-b) Synthesis of 2-fluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the above formula (204):
    First, 10.0 g of 4-bromo-2-fluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from the above synthesis (4-a), 9.43 g of tributylvinyltin, 0.58 g of Tetrakis (triphenylphosphine) palladium (0), 0.03 g of p-methoxyphenol and 150 ml of anhydrous toluene were placed in an argon-substituted 300 ml flask and stirred at reflux for 18 hours. After stirring, the insoluble material was filtered off and ether was added to the filtrate to separate the organic layer. The organic layer was washed with 5% ammonia water, further washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to yield 6.72 g (Y: 77.3%) of 2-fluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinyl ratio. Phenyl was obtained. The purity of the obtained compound was 100.0% in GC, 99.9% in HPLC, and 1 spot in TLC. The phase transition temperatures of the resulting compounds are as follows:
    29.1 ℃ 52.8 ℃
    Crystal ---> Smectic X Award ---> Nematic Award
    137.2 ℃
    ---> Polymerization
    From the IR measurement and mass spectrometry, a molecular ion peak was identified at 350, and the resultant material was found to be a compound of formula (204) in view of the raw material used.
    Synthesis Example 5 Synthesis of Polymerizable Compound 2,6-Difluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Chemical Formula (205):
    (5-a) Chemical formula Synthesis of compound 4-bromo-2,6-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 50 ml of ethanol in which 5.61 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid was dissolved, and 50 ml of 5.0 g of 4-bromo-2,6-difluoro-1-iodobenzene dissolved in Benzene, 2.0 mol / l aqueous 15.7 ml sodium carbonate solution and 0.45 g tetrakis (triphenylphosphine) palladium (0) were placed in an argon-substituted 200 ml flask and stirred for 48 hours at reflux. After the reaction, water and ether were added to the reaction solution to perform extraction. The resulting ether layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from acetone to give 2.58 g (Y: 39.1%) of 4-bromo-2,6-difluoro-4 '-(trans-4-pentyl Cyclohexyl) biphenyl was obtained. The purity of the obtained compound was 100.0% in GC.
    (5-b) Synthesis of Polymerizable Compound 2,6-difluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by Formula (205):
    First, 2.58 g of 4-bromo-2,6-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from the above synthesis (5-a), 2.33 g of tributylvinyl tin, 0.18 g of tetrakis (triphenylphosphine) palladium (0), 0.008 g of p-methoxyphenol and 50 ml of anhydrous toluene were placed in an argon-substituted 300 ml flask and stirred under reflux for 9 hours. After the reaction, the insoluble material was filtered off, and 100 ml of water in which 50 ml of ether and 1.73 g of potassium fluoride were dissolved was added to the filtrate and stirred. After stirring, the insoluble material was again filtered off and the organic layer was separated. The organic layer was washed with 5% ammonia water, further washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to yield 1.57 g (Y: 69.6%) of 2,6-difluoro-4 '-(trans-4-pentylcyclohexyl) -4. -Vinylbiphenyl was obtained. The purity of the obtained compound was 100.0% in GC, 99.7% in HPLC and 1 spot in TLC. The phase transition temperatures of the resulting compounds are as follows:
    62.3 ℃ 116.0 ℃
    Crystalline ---> Nematic Phase ---> Polymerization
    From the IR measurement and mass spectrometry, a molecular ion peak was identified at 368, and the resultant material was found to be a compound of formula (205) in view of the raw material used.
    Synthesis Example 6 Synthesis of Polymerizable Compound 3-Fluoro-4 ′-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Formula (206):
    (6-a) Chemical formula Synthesis of compound 4-bromo-3-fluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 100 ml of ethanol in which 11.89 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid was dissolved, 100 ml of benzene in which 10.0 g of 1-bromo-2-fluoro-4-iodobenzene was dissolved, 33.2 ml aqueous sodium carbonate and 0.96 g tetrakis (triphenylphosphine) palladium (0) at a concentration of 2.0 mol / l were placed in an argon-substituted 500 ml flask and stirred for 16 hours under reflux. After the reaction, water and ether were added to the reaction solution to perform extraction. The resulting ether layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from acetone to give 11.6 g (Y: 86.8%) of 4-bromo-3-fluoro-4 '-(trans-4-pentylcyclohexyl). Biphenyl was obtained. The purity of the obtained compound was 100.0% in GC.
    (6-b) Synthesis of 3-fluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the formula (206):
    First, 5.0 g of 4-bromo-3-fluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from the above synthesis (6-a), 4.72 g of tributylvinyl tin, 0.36 g of Tetrakis (triphenylphosphine) palladium (0), 0.015 g of p-methoxyphenol and 50 ml of anhydrous toluene were placed in an argon-substituted 300 ml flask and stirred at reflux for 8 hours. After the reaction, the insoluble material was filtered off, and 100 ml of water in which 10 ml of ethyl acetate and 1.73 g of potassium fluoride were dissolved was added to the filtrate and stirred. After stirring, the insoluble material was again filtered off and the organic layer was separated. The organic layer was washed with 5% ammonia water, further washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to give 2.99 g (Y: 68.8%) of 3-fluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinyl ratio. Phenyl was obtained. The purity of the obtained compound was 100.0% in GC, 99.3% in HPLC, and 1 spot in TLC. The phase transition temperatures of the resulting compounds are as follows:
    102.0 ℃ 104.9 ℃
    Crystal ---> Smectic A Award ---> Nematic Award
    108.9 ℃
    ---> Polymerization
    From the IR measurement and mass spectrometry, a molecular ion peak was identified at 350, and the resultant material was found to be a compound of formula (206) in view of the raw material used.
    Synthesis Example 7 Synthesis of Polymerizable Compound 2,5-Difluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Chemical Formula (207):
    (7-a) Chemical formula Synthesis of compound 2,5-difluoro-4-nitro-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 50 ml of ethanol in which 7.52 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid was dissolved, and 50 ml of 5.0 g of 4-bromo-2,5-difluoro-1-nitrobenzene dissolved in Benzene, 21.0 ml aqueous sodium carbonate solution at 2.0 mol / l and 0.61 g tetrakis (triphenylphosphine) palladium (0) were placed in an argon-substituted 200 ml flask and stirred at reflux for 12 hours. After the reaction, water and ether were added to the reaction solution to perform extraction. The resulting ether layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/4) and recrystallized from hexane to give 6.87 g (Y: 84.4%) of 2,5-difluoro-4-nitro-4 '-( Trans-4-pentylcyclohexyl) biphenyl was obtained. The purity of the obtained compound was 100.0% in GC. The phase transition temperature of this compound is as follows:
    58.4 ℃ 108.3 ℃
    Crystal ---> Nematic Award ---> Isotropic
    (7-b) chemical formula Synthesis of compound 4-amino-2,5-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 6.86 g of 2,5-difluoro-4-nitro-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from the above synthesis (7-a), 1.25 g of 10% palladium carbon and 100 ml Tetrahydrofuran was placed in a 200 ml autoclave. The autoclave was charged with hydrogen under a pressure of 10 kg / cm 2 and stirred at room temperature for 6 hours. After the reaction, palladium carbon was filtered off and the solvent was distilled off from the filtrate. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 4/1) and recrystallized from hexane to give 5.61 g (Y: 88.6%) of 4-amino-2,5-difluoro-4'-. (Trans-4-pentylcyclohexyl) biphenyl was obtained. The purity of the obtained compound was 100.0% in GC and the melting point was 68.3 to 70.4 ° C.
    (7-c) chemical formula Synthesis of compound 4-bromo-2,5-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by:
    First, 8.1 ml of concentrated sulfuric acid, 1.1 g of sodium nitrite and 20 ml of acetic acid were placed in a 50 ml flask under cooling. Then 5.2 g of 4-amino-2,5-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from the above synthesis (7-b) were added as crystals to the mixture, Stir until the crystals dissolve and diazotize.
    2.5 g of copper bromide, 6.6 ml of hydrobromic acid and 20 ml of acetic acid were then placed in a 100 ml flask. The diazo compound solution was added dropwise to the mixture and stirred for 24 hours. After the reaction, ether and 21 ml of 50% sodium hydroxide were added to the reaction solution, and then sodium carbonate was added to neutralize the reaction solution to separate the ether layer. The obtained ether layer was washed with 1N aqueous potassium carbonate solution and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from acetone to give 3.7 g (Y: 61.0%) of 4-bromo-2,5-difluoro-4 '-(trans-4-pentyl). Cyclohexyl) biphenyl was obtained. The purity of the obtained compound was 99.6% in GC.
    (7-d) Synthesis of 2,5-difluoro-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the above formula (207):
    First, 3.74 g of 4-bromo-2,5-difluoro-4 '-(trans-4-pentylcyclohexyl) biphenyl obtained from the above synthesis (7-c), 3.52 g of tributylvinyl tin, 0.26 g tetrakis (triphenylphosphine) palladium (0), 0.011 g p-methoxyphenol and 100 ml anhydrous toluene were placed in an argon-substituted 100 ml flask. The resulting mixture was heated to 105 ° C. and stirred for 8 hours. After the reaction, the insoluble material was filtered off and 200 ml of water containing 3.4 g of potassium fluoride was added to the filtrate and stirred for 6 hours. After stirring, the insoluble material was again filtered off and ether was added to the filtrate to separate the organic layer. The resulting organic layer was washed with 5% ammonia water, further washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from acetone to give 2.7 g (Y: 82.5%) of 2,5-difluoro-4 '-(trans-4-pentylcyclohexyl) -4 -Vinylbiphenyl was obtained. The purity of the obtained compound was 99.5% in GC, 99.5% in HPLC and 1 spot in TLC. The phase transition temperatures of the resulting compounds are as follows:
    45.3 ℃ 123.1 ℃
    Crystalline ---> Nematic Phase ---> Polymerization
    From the IR measurement and mass spectrometry, a molecular ion peak was identified at 368, and the resultant material was found to be a compound of formula (207) in view of the raw material used.
    Synthesis Example 8 Synthesis of Polymerizable Compound 2,3-Difluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -4-vinylbenzene represented by the following general formula (208):
    (8-a) Chemical formula Synthesis of compound 1,2-difluoro-3- [4- (trans-4-propylcyclohexyl) cyclohexenyl] benzene represented by:
    First, 46 g of 1,2-difluorobenzene and 240 ml of anhydrous tetrahydrofuran were placed in an argon-substituted 2 L flask and cooled to -60 ° C. Thereafter, 315 ml of a hexane solution containing n-butyllithium at a concentration of 1.6 mol / l was added dropwise to the mixture with stirring for 1 hour, and further stirred for 2 hours while maintaining the same temperature. Thereafter, 470 ml of anhydrous tetrahydrofuran in which 80 g of 4- (trans-4-propylcyclohexyl) cyclohexane was dissolved was added dropwise while stirring at the same temperature. The resulting mixture was slowly cooled to room temperature, stirred for 8 hours, and then cooled to 0 ° C. The reaction solution was poured into dilute hydrochloric acid to acidify the reaction solution. Toluene was added to the obtained solution and extraction was performed. The resulting toluene layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue, 2 g of p-toluenesulfonic acid and 1 L of toluene were placed in a 2 L flask equipped with a water metering tube and subjected to azeotropic dehydration for 5 hours under reflux. After the reaction, the reaction solution was washed with saturated brine and dried over sodium sulfate. Thereafter, the solvent was distilled off. The residue was distilled (boiling point 151 ° C./16 pa) and recrystallized from acetone to give 55.7 g (Y: 48.6%) of 1,2-difluoro-3- [4- (trans-4-propylcyclohexyl) cyclohexenyl ] Benzene was obtained. The purity of the obtained compound was 98.0% in GC.
    (8-b) chemical formula Synthesis of compound 1,2-difluoro-3- [4- (trans-4-propylcyclohexyl) cyclohexyl] benzene represented by:
    First, 55.7 g of 1,2-difluoro-3- [4- (trans-4-propylcyclohexyl) cyclohexenyl] benzene obtained from the above synthesis (8-a), 4.3 g of 10% palladium carbon and 550 ml of ethyl acetate was placed in a 1 L autoclave. The autoclave was charged with hydrogen to maintain a pressure of 3 kg / cm 2 and the mixture was stirred at room temperature for 3 hours. After the reaction, palladium carbon was filtered off and the solvent was distilled off from the filtrate. The residue, 30 g of potassium t-butoxide and 200 ml of anhydrous dimethyl sulfoxide were placed in an argon-substituted 500 ml flask and stirred at 35 ° C. for 3 hours. After the reaction, dilute hydrochloric acid was poured into the reaction solution to acidify the reaction solution. Toluene was added to the obtained solution and extraction was performed. The resulting toluene layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was recrystallized from acetone to give 40.0 g (Y: 71.4%) of 1,2-difluoro-3- [4- (trans-4-propylcyclohexyl) cyclohexyl] benzene. The purity of the obtained compound was 99.0% in GC.
    (8-c) chemical formula Synthesis of Compound 1-acetyl-2,3-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene represented by:
    First, 5.9 g of anhydrous aluminum chloride and 30 ml of methylene chloride were placed in a 100 ml flask. Thereafter, 3.5 g of acetyl chloride was added dropwise to the mixture at 5 DEG C or lower, and stirred for 30 minutes while maintaining the same temperature. Then, 11.8 g of 1,2-difluoro-3- [4- (trans-4-propylcyclohexyl) cyclohexyl] benzene obtained in the above synthesis (8-b) was added to the mixture at 5 ° C. or lower. And stirred at room temperature for 30 minutes. After the reaction, the reaction solution was poured into dilute hydrochloric acid to separate the organic layer. The obtained organic layer was washed with water and dried over sodium sulfate. Then, the solvent was distilled off. The residue was recrystallized from acetone to give 5.6 g (Y: 42.1%) of 1-acetyl-2,3-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene. . The purity of the obtained compound was 99.4% in GC.
    (8-d) Chemical formula Synthesis of Compound 1- (1-hydroxyethyl) -2,3-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene represented by:
    First, 0.1 g of lithium aluminum hydride and 20 ml of anhydrous tetrahydrofuran were placed in a 200 ml flask. Thereafter, 1.78 g of 1-acetyl-2,3-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene obtained in Synthesis (8-c) was dissolved. 40 ml of anhydrous tetrahydrofuran was added dropwise with stirring to the mixture and stirred under reflux for 6 hours. After the reaction, 3N hydrochloric acid was added to the reaction solution to acidify the reaction solution, thereby inactivating unreacted lithium aluminum hydride. Ether layer was separated by adding ether to the reaction solution. The obtained ether layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 4/1) to give 1.41 g (Y: 78.8%) of 1- (1-hydroxyethyl) -2,3-difluoro-4 -[Trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. The purity of the obtained compound was 99.5% in GC.
    (8-e) of the polymerizable compound 2,3-difluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexenyl] -4-vinylbenzene represented by the formula (208) synthesis:
    First, 1.49 g of 1- (1-hydroxyethyl) -2,3-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl obtained in Synthesis (8-d) ] Benzene, 0.08 g potassium hydrogensulfate, 0.05 g p-methoxyphenol and 50 ml benzene were placed in a 200 ml flask equipped with a water metering tube and subjected to azeotropic dehydration for 16 hours under reflux. After the reaction, the reaction solution was washed with water and dried over sodium sulfate. Thereafter, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to give 0.70 g (Y: 21.1%) of 2,3-difluoro-1- [trans-4- (trans-4-propylcyclo). Hexyl) cyclohexenyl] -4-vinylbenzene was obtained. The purity of the obtained compound was 100.0% in GC, 99.9% in HPLC, and 1 spot in TLC. The phase transition temperatures of the resulting compounds are as follows:
    42.9 ℃ 160 ℃
    Crystalline ---> Nematic Phase ---> Polymerization
    From the IR measurement and mass spectrometry, a molecular ion peak was identified at 346, and the resultant material was found to be a compound of formula (208) in view of the raw material used.
    Synthesis Example 9 Synthesis of Polymerizable Compound 3-Methyl-4 ′-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Formula (209):
    (9-a) Chemical formula Synthesis of Compound 4-Bromo-2-methylphenol Represented by:
    First, 70 ml of water, 25 ml of concentrated sulfuric acid and 25.0 g of 4-bromo-2-methylaniline were placed in a 500 ml flask. After adding 60 g of ice, 30 ml of water in which 10.9 g of sodium nitrite was dissolved was added dropwise for 25 minutes while maintaining the temperature below 5 ° C. Then 100 ml of water, 100 g of ice and 1 g of urea were added and the resulting mixture was left for 30 minutes. Thereafter, 50 g of anhydrous sodium sulfate, 70 ml of concentrated sulfuric acid, and 33 ml of water were placed in a 500 ml flask equipped with a still, and heated to 130 to 135 ° C. The former reaction solution was added dropwise to the mixture obtained above, and the resulting phenol was distilled off with water vapor. Extraction was performed by adding ether to the distilled solution. The resulting ether layer was washed with water and aqueous sodium hydrocarbon solution. Extraction was performed by further adding 10% aqueous sodium hydroxide solution. Then, 35 ml of concentrated hydrochloric acid was added to the aqueous sodium hydroxide solution obtained above to acidify the solution, and ether was added to extract. The resulting ether layer was washed with water and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure. The residue was distilled (boiling point 135-139 ° C./8 mmHg) to give 17.48 g (Y: 69.7%) of 4-bromo-2-methylphenol. The purity of the obtained compound was 98.8% in GC.
    (9-b) Formula Synthesis of compound 4-bromo-2-methylphenyl methoxymethyl ether represented by:
    First, 80 ml of anhydrous methanol was put into a 300 ml flask equipped with a calcium chloride tube. Then, 2.15 g of metallic sodium was added and 25 ml of anhydrous methanol containing 17.48 g of 4-bromo-2-methylphenol obtained in the above synthesis (9-a) was added dropwise to the mixture, and the mixture was added. Stir for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure. 130 ml of toluene was added to the residue and the solvent was distilled off again under reduced pressure. In the state substituted with argon, 75 ml of anhydrous tetrahydrofuran was added to the residue and 8.28 g of chloromethyl methyl ether was added dropwise for 15 minutes under cooling. The resulting mixture was stirred while maintaining the temperature for 30 minutes and further stirred at room temperature for 30 minutes. 200 ml of 2% aqueous sodium hydroxide solution was added to the reaction solution, and ether extraction was performed. The resulting ether layer was washed with water and brine, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off. The residue was distilled (boiling point of 142 to 150 ° C./8 mm Hg) to give 18.03 g (Y: 83.4%) of 4-bromo-2-methylphenol methoxymethyl ether. The purity of the obtained compound was 92.7% in GC.
    (9-c) Synthesis of compound 4 '-(trans-4-pentylcyclohexyl) -3-methylbiphenyl-4-yl methoxymethyl ether represented by the following formula:
    First, 125 ml of ethanol containing 21.1 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid in an argon-substituted 500 ml flask, 4-bromo-2-methylphenylmethacrylate synthesized in the above (9-c) 125 ml of benzene in which 16.2 g of methoxymethyl was dissolved, 77.0 ml of an aqueous sodium carbonate solution at a concentration of 2 mol / liter, and 2.02 g of tetrakis (triphenylphosphine) palladium (0) were charged and stirred at reflux for 5 hours. After the reaction was completed, water and toluene were added to the reaction solution and extracted. The obtained toluene layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/1) to give 21.36 g of 4 '-(trans-4-pentylcyclohexyl) -3-methylbiphenyl-4-yl methoxymethyl ether. (Y: 80.2%) was obtained. The purity of the obtained compound was 97.2%, as measured by GC.
    (9-d) Synthesis of Compound 4- [4- (trans-4-pentylcyclohexyl) phenyl] -2-methylphenol represented by the following formula:
    First, 21.36 g of 4 '-(trans-4-pentylcyclohexyl) -3-methylbiphenyl-4-yl methoxymethyl ether synthesized in the above (9-d) in a 300 ml flask, 50 ml of 6 N hydrochloric acid, Charge 100 ml of tetrahydrofuran and 10 ml of isopropyl alcohol and stir for 2 hours under reflux. After the reaction was completed, water and toluene were added to the reaction solution and extracted. The obtained toluene layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was recrystallized from methanol to give 15.34 g (Y: 81.3%) of 4- [4-trans-4-pentylcyclohexyl) phenyl] -2-methylphenol. The purity of the obtained compound was 99.8%, as measured by GC.
    (9-e) Synthesis of compound 4- [4- (trans-4-pentylcyclohexyl) phenyl] -2-methylphenyl trifluoromethanesulfonate represented by the following formula:
    First, 10.1 g of 4- [4-trans-4-pentylcyclohexyl) phenyl] -2-methylphenol synthesized in the above (9-c) and 50 ml of pyridine were charged into a 200 ml flask equipped with a calcium chloride tube, The mixture was further cooled to -20 ° C. Thereafter, 9.31 g of trifluoromethanesulfonic anhydride was added dropwise to the mixture with stirring. After completion of the dropwise addition, the resulting mixture was stirred at 0 ° C. for 24 hours. The reaction solution was poured into water, followed by extraction with ether. The resulting ether layer was washed with 5% hydrochloric acid, then further with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) to give 13.38 g (Y: 95.2%) of 4- [4-trans-4-pentylcyclohexyl) phenyl] -2-methylphenyl trifluoromethanesulfonate. Got it. The purity of the obtained compound was 85.8%, as measured by GC.
    (9-f) Synthesis of the polymerizable compound 3-methyl-4 '(trans-4-pentylcyclohexyl) 4-vinylbiphenyl represented by the above formula (209):
    First, 9.87 g of 4- [4-trans-4-pentylcyclohexyl) phenyl] -2-methylphenyl trifluoromethanesulfonate synthesized in the above (9-e) in a 100 ml flask substituted with argon, tributylvinyl 8.01 g of tin, tris (dibenzylideneacetone) (chloroform) dipalladium (0) 0.21 g, 0.19 g of tri (2-furyl) phosphine, 2.36 g of lithium chloride, 2,6-di-tert-butyl-p-cre Determination of the Sol Several debris and 37 ml of dehydrated N-methylpyrrolidone were charged and stirred at 50 ° C. for 8 hours. After the reaction was completed, saturated aqueous potassium fluoride solution and hexane were added to the reaction solution, followed by stirring for 1 hour. Thereafter, the insolubles were separated by filtration, and the filtrate was separated to obtain an organic layer. The organic layer was then washed with 5% ammonia water and further with saturated brine, and then dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to give 5.20 g (Y: 71.1%) of 3-methyl-4 '(trans-4-pentylcyclohexyl) -4-vinylbiphenyl. Got. The purity of the obtained compound was 99.8% as determined by GC, 100.0% as determined by HPLC, and was found to be 1 point as measured by TLC. In addition, the phase transition temperatures of this compound were as follows:
    IR measurement results and mass spectrometry confirmed the molecular ion peak at 346 and, considering the raw materials used, confirmed that the resulting material was the compound represented by the formula (209).
    Synthesis Example 10 Synthesis of Polymerizable Compound 4-cyclohexyl-4-vinylbiphenyl Represented by the following Formula (210):
    (10-a) Synthesis of Compound 4-Bromo-1-benzyloxybenzene represented by the following formula:
    First, 53.2 g of benzyl chloride, 69.2 g of 4-bromophenol, 110.4 g of potassium carbonate and 800 ml of methylethyl ketone were charged to a 2-liter flask and stirred for 30 minutes under reflux. After the reaction was completed, the insolubles were separated by filtration and the solvent was evaporated from the filtrate. Ether and 2% aqueous sodium hydroxide solution were added to the residue to separate the organic layer. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. This residue was evaporated (boiling point of 131 ° C to 140 ° C / 0.08 mmHg) to give 61.0 g of 4-bromo-1-benzyloxybenzene (Y: 58.07%). The purity of the obtained compound was 99.0% as measured by GC.
    (10-b) Synthesis of compound 4-benzyloxyphenylboronic acid represented by the following formula:
    First, 5.07 g of magnesium and 80 ml of dehydrated tetrafuran were charged into a 500 ml flask substituted with argon. Several fragments of iodine were added to the mixture to activate magnesium. Thereafter, 100 ml of dehydrated tetrahydrofuran in which 45.7 g of 4-bromo-1-benzeloxybenzene synthesized in the above (10-a) was dissolved was added dropwise to the mixture while stirring. After completion of the dropwise addition, the mixture was stirred at reflux for 30 minutes, and the reaction solution was cooled to -40 ° C. Thereafter, 60 ml of dehydrated tetrahydrofuran in which 21.66 g of trimethyl borate was dissolved was added dropwise to the reaction solution with stirring. After gradually warming to room temperature, the reaction solution was stirred at reflux for 30 minutes. Thereafter, the mixture was cooled to 0 ° C. again, and 200 ml of 10% sulfuric acid was added thereto, followed by stirring for 1 hour. Toluene was added to the reaction solution to separate the organic layer. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was recrystallized from toluene to obtain 36.5 g (Y: 92.1%) of 4-benzeneoxyphenylboronic acid.
    (10-c) Synthesis of compound 4-benzyloxy-4'-cyclohexylbiphenyl represented by the following formula:
    First, 80 ml of ethanol in which 7.18 g of 4-benzyloxyphenylboronic acid synthesized in the above (10-b) and 5.00 g of 1-bromo-4-cyclohexylbenzene were dissolved in a 200 ml flask substituted with argon. 21.0 ml of an aqueous solution of sodium carbonate at a concentration of 2 mol / liter, and 0.24 g of tetrakis (triphenylphosphine) palladium (0) were charged and stirred under reflux for 8 hours. After the reaction was completed, water and toluene were added to the reaction solution and extracted. The resulting toluene layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/4) to give 5.04 g (Y: 70.1%) of 4-benzyloxy-4'-cyclohexylbiphenyl. The purity of the obtained compound was 98.3% as measured by GC.
    (10-d) Synthesis of compound 4-cyclohexyl-4'-hydroxybiphenyl represented by the following formula:
    First, 5.04 g of 4-benzyloxy-4'-cyclohexylbiphenyl synthesized in the above (10-c), 0.52 g of 10% palladium carbon and 100 ml of tetrahydrofuran were charged to a 200 ml autoclave. After charging to maintain a hydrogen pressure of 10 kg / cm 2 , the mixture was stirred at room temperature for 48 hours. After the reaction was completed, palladium carbon was separated by filtration and the solvent was evaporated from the filtrate. The residue was recrystallized from a mixed solvent of acetone / hexane (1/3) to obtain 3.01 g (Y: 95.6%) of 4-cyclohexyl-4'-hydroxybiphenyl. The purity of the obtained compound was 100.0% as measured by GC.
    (10-e) Synthesis of Compound 4'-cyclohexylbiphenyl-4-yl trifluoromethanesulfonate represented by the following formula:
    First, 2.95 g of 4-cyclohexyl-4'-hydroxybiphenyl synthesized in the above (10-d) and 50 ml of pyridine were charged into a 100 ml flask equipped with a calcium chloride tube, and the temperature of the mixture was -20. Cool to C. Then, 5.65 g of trifluoromethanesulfonic anhydrides were dripped at this mixture, stirring. After completion of the dropwise addition, the resulting mixture was stirred at 0 ° C. for 24 hours. The reaction solution was poured into water, and ether was added for extraction. The ether layer was washed with 5% hydrochloric acid, further washed with saturated brine, and then dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) to obtain 3.49 g (Y: 77.7%) of 4'-cyclohexylbiphenyl-4-yl trifluoromethanesulfonate. The purity of the obtained compound was 100.0% as measured by GC.
    (10-f) Synthesis of the polymerizable compound 4-cyclohexyl-4'-vinylbiphenyl represented by Chemical Formula (210):
    First, in a 100 ml flask substituted with argon, 3.49 g of 4'-cyclohexylbiphenyl-4-yl trifluoromethanesulfonate synthesized in the above (10-e), 3.45 g of tributylvinyl tin, tris (dibenzyl) Lidenacetone) (chloroform) dipalladium (0) 0.09 g, tri (2-furyl) phosphine 0.04 g, lithium chloride 1.15 g, 2,6-di-tert-butyl-p-cresol crystal Several fragments and dehydrated N Charge 30 ml of methylpyrrolidone and stir at 50 ° C. for 10 hours. After the reaction was completed, saturated aqueous potassium fluoride solution and hexane were added to the reaction solution, followed by stirring for 1 hour. Insoluble matters were separated by filtration, and the organic layer was separated from the filtrate obtained. Thereafter, the organic layer was washed with 5% ammonia water, further washed with saturated brine, and then dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to obtain 1.82 g (Y: 76.4%) of 4-cyclohexyl-4'-vinylbiphenyl. The purity of the obtained compound was 100.0% as determined by GC, 99.9% as measured by HPLC, and was found to be 1 point as measured by TLC. In addition, the phase transition temperatures of this resulting compound were as follows:
    IR measurement results and mass spectrometry confirmed the molecular ion peak at 263 and considering the raw materials used, it was confirmed that the resulting material was the compound represented by the formula (210).
    Synthesis Example 11 Synthesis of Compound 2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Formula (211):
    (11-a) Synthesis of Compound 4 '-(trans-4-pentylcyclohexyl) -2-trifluoromethyl-4-nitrobiphenyl represented by the following formula:
    First, benzene in which 100 ml of ethanol dissolved in 6.57 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid and 10.0 g of 2-trifluoromethyl-4-nitrobromobenzene were dissolved in a 300 ml flask substituted with argon. 100 ml, 37 ml of concentration 2 mol / liter aqueous sodium carbonate solution and 1.07 g of tetrakis (triphenylphosphine) palladium (0) were charged and stirred under reflux for 12 hours. After the reaction was completed, water and ether were added to the reaction solution and extracted. The resulting ether layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane / toluene = 4/1) to give 14.2 g of 4 '-(trans-4-pentylcyclohexyl) -2-trifluoromethyl-4-nitrobiphenyl ( Y: 91.3%). The purity of the obtained compound was 100.0% as measured by GC.
    (11-b) Synthesis of compound 4-amino-2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by the following formula:
    First, 14.19 g of 4 '-(trans-4-pentylcyclohexyl) -2-trifluoromethyl-4-nitrobiphenyl synthesized in (11-a) in a 500 ml autoclave, 1.20 g and 100 ml of tetrahydrofuran were charged. After charging to maintain a hydrogen pressure of 10 kg / cm 2 , the mixture was stirred at room temperature for 3 days. After completion of the reaction, palladium carbon was separated by filtration and the solvent was evaporated from the filtrate. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 4/1) to give 12.8 g of 4-amino-2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl. (Y: 87.5%) was obtained. The purity of the obtained compound was 100.0% as measured by GC.
    (11-c) Synthesis of compound 4-bromo-2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by the following formula:
    First, 18.3 ml of concentrated sulfuric acid was charged into a 300 ml flask, and 2.5 g of sodium nitrite was added in a solid state while cooling and stirring. The mixture was stirred for 30 minutes, and then 100 ml of acetic acid was added while cooling. Then, 12.85 g of 4-amino-2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl synthesized in (11-b) was added to the mixture in a solid state at room temperature, Furthermore, it stirred until it dissolved, and the said mixture was subjected to the diazotization reaction. Thereafter, 5.68 g of cuprous bromide, 18.7 ml of 48% bromic acid and 100 ml of acetic acid were charged into a 500 ml eggplant flask. The diazo compound solution described above was added dropwise to the mixture and stirred at room temperature for 24 hours. After the reaction was completed, diethyl ether and 303 ml of a 50% sodium hydroxide aqueous solution were added to the reaction solution, and sodium carbonate was added until the pH became 7. The ether layer was separated from the reaction solution. The ether layer was washed with 1N aqueous potassium carbonate solution and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent; hexane) to give 11.81 g (Y: 74.7%) of 4-bromo-2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl. Got. The purity of the obtained compound was 100.0%, as measured by GC, and the melting point was 51 to 52 ° C.
    (11-d) Synthesis of Polymerizable Compound 2-Trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by Formula (211):
    First, 3.74 g of 4-bromo-2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl synthesized in the above (11-c) in a 100 ml flask substituted with argon, tributyl 4.20 g of vinyl tin, 0.13 g of tetrakis (triphenylphosphine) palladium (0), 0.02 g of p-methoxyphenol and 50 ml of dehydrated toluene were charged, heated to 115 ° C. and stirred for 8 hours. After completion of the reaction, the insolubles were separated by filtration, and 100 ml of water in which 1.7 g of potassium fluoride was dissolved was added to the filtrate, followed by stirring for 6 hours. The insolubles were again filtered off and ether was added to the filtrate to separate the organic layer. The organic layer was washed with 5% ammonia water and then with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane), recrystallized from acetone, and 3.43 g of 2-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl (Y : 77.6%). The purity of the obtained compound was 100.0% as determined by GC, 99.8% as measured by HPLC, and was found to be 1 point as measured by TLC. In addition, the phase transition temperatures of this compound were as follows:
    IR measurement results and mass spectrometry confirmed the molecular ion peak at 400 and considering the raw materials used, it was confirmed that the resulting material was the compound represented by the above formula (211).
    Synthesis Example 12 Synthesis of Polymerizable Compound 3-Trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by the following Chemical Formula (212):
    (12-a) Synthesis of Compound 4-amino-4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethylbiphenyl represented by the following formula:
    First, 100 ml of ethanol containing 4.91 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid and 10.0 g of 2-trifluoromethyl-4-bromoaniline were dissolved in a 300 ml flask substituted with argon. 4 ml ml of an aqueous solution of sodium carbonate at a concentration of 2 mol / liter and 1.20 g of tetrakis (triphenylphosphine) palladium (0) were charged and stirred under reflux for 6 hours. After the reaction was completed, water and ether were added to the reaction solution and extracted. The ether layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane / toluene = 4/1) to give 14.82 g of 4-amino-4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethylbiphenyl. Y: 91.3%). The purity of the obtained compound was 99.2% as measured by GC.
    (12-b) Synthesis of compound 4-bromo-3-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl represented by the following formula:
    First, 21.1 ml of concentrated sulfuric acid was charged into a 300 ml flask, and 2.89 g of sodium nitrite was added in a solid state while cooling and stirring. The mixture was stirred for 30 minutes and then 100 ml of acetic acid was added while cooling. Thereafter, 14.82 g of 4-amino-4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethylbiphenyl synthesized in (12-a) was added to the mixture in a solid state at room temperature, Furthermore, it stirred until it dissolved, and the said mixture was subjected to the diazotization reaction. Thereafter, 6.55 g of cuprous bromide, 21.5 ml of 48% bromic acid, and 100 ml of acetic acid were charged to a 500 ml flask. The solution of the diazo compound described above was added dropwise to the mixture and stirred at room temperature for 24 hours. After the completion of the reaction, 417 ml of diethyl ether and 50% aqueous sodium hydroxide solution were added to the reaction solution, and sodium carbonate was added until the pH became 7. The ether layer was separated from the reaction solution. The ether layer was washed with 1N aqueous potassium carbonate solution and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) to give 4.94 g (Y: 28.6%) of 4-bromo-3-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl. Got. The purity of the obtained compound was 99.1%, as measured by GC.
    (12-c) Synthesis of Polymerizable Compound 3-Trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl represented by Chemical Formula (212):
    First, 4.94 g of 4-bromo-3-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) biphenyl synthesized in the above (12-b) in a 100 ml flask substituted with argon, tributyl 4.14 g of vinyl tin, 0.13 g of tetrakis (triphenylphosphine) palladium (0), 0.02 g of p-methoxyphenol and 50 ml of dehydrated toluene were charged, heated to 115 ° C. and stirred for 8 hours. After the reaction was completed, insoluble materials were separated by filtration, and 100 ml of water in which 1.7 g of potassium fluoride was dissolved was added to the filtrate, followed by stirring for 6 hours. The insolubles were filtered off again, and ether was added to the filtrate to separate the organic layer. The organic layer was washed with 5% ammonia water and then with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to give 3.03 g of 3-trifluoromethyl-4 '-(trans-4-pentylcyclohexyl) -4-vinylbiphenyl (Y : 69.4%). The purity of the obtained compound was 99.4% as determined by GC, 99.0% as measured by HPLC, and was found to be 1 point as measured by TLC. In addition, the phase transition temperatures of this compound were as follows:
    IR measurement results and mass spectrometry confirmed a molecular ion peak at 400, and considering the raw materials used, it was confirmed that the resulting material was the compound represented by Chemical Formula 212.
    Synthesis Example 13 Synthesis of Compound 4'-perfluorobutyl-4-vinylbiphenyl represented by the following Formula (213):
    (13-a) Synthesis of Compound 4-benzyloxy-4'-bromobiphenyl represented by the following formula:
    First, 25.0 g of benzylbromide, 36.42 g of 4'-bromo-4-hydroxybiphenyl, 36.4 g of potassium carbonate, and 300 ml of methylethyl ketone were charged to a 1 liter flask, and stirred at reflux for 6 hours. After the reaction was completed, 300 ml of tetrahydrofuran was added to the reaction solution, and the mixture was cooled to ambient temperature. Insoluble matter was separated by filtration, and toluene was added to the filtrate to separate the organic layer. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was recrystallized from acetone to give 42.56 g (Y: 85.8%) of 4-benzyloxy-4'-bromobiphenyl. The purity of the obtained compound was 99.0% as measured by GC.
    (13-b) Synthesis of Compound 4-benzyloxy-4'-perfluorobutylbiphenyl represented by the following formula:
    First, 13.5 g of 4-benzyloxy-4'-bromobiphenyl synthesized in the above (13-a), 12.65 g of copper powder and 40 ml of dehydrated dimethisulfoxide were charged to a 200 ml flask, and further 60 ° C. Heated to. Then 15.15 g of perfluorobutyl iodide was added to the mixture. The mixture was kept at the same temperature for 2 hours, slowly warmed up to 110 ° C. and then stirred for 4 hours. Thereafter, the mixture was cooled to 60 ° C, and 6.90 g of perfluorobutyl iodide and 6.83 g of copper powder were added to the mixture, which were gradually warmed up to 110 ° C, and then stirred for 6 hours. After the reaction was completed, chloroform was added to the reaction solution, followed by stirring. The insolubles were separated by filtration, and the filtrate was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane / toluene = 6/1) and recrystallized from acetone to give 17.08 g of 4-benzyloxy-4'-perfluorobutylbiphenyl (Y: 89.7%). Got it. The purity of the obtained compound was 96.2%, as measured by GC, and the melting point was 128 to 134 占 폚.
    (13-c) Synthesis of Compound 4'-perfluorobutyl-4-hydroxybiphenyl represented by the following formula:
    First, 16.6 g of 4-benzyloxy-4'-perfluorobutylbiphenyl synthesized in the above (13-b), 1.0 g of 10% palladium carbon and 100 ml of tetrahydrofuran were charged into a 500 ml autoclave. After charging hydrogen into the autoclave so that the hydrogen pressure became 3 kg / cm 2 , the mixture was stirred at room temperature for 24 hours. After completion of the reaction, palladium carbon was separated by filtration and the solvent was evaporated from the filtrate. The residue was recrystallized from toluene to give 9.35 g (Y: 69.4%) of 4'-perfluorobutyl-4-hydroxybiphenyl. The purity of the obtained compound was 98.3%, as measured by GC, and the melting point was 131 to 134 占 폚.
    (13-d) Synthesis of 4'-perfluorobutylbiphenyl-4-yl trifluoromethanesulfonate represented by the following formula:
    First, 1.24 g of 4'-perfluorobutyl-4-hydroxybiphenyl and 50 ml of pyridine synthesized in the above (13-c) were charged to a 100 ml flask equipped with a calcium chloride tube, and cooled to -20 ° C. I was. Thereafter, 1.09 g of trifluoromethanesulfonic anhydride was added dropwise while stirring. After completion of dropping, the mixture was stirred at 0 ° C. for 24 hours. The reaction solution was poured into water, and ether was added for extraction. The ether layer was washed with 5% hydrochloric acid, further washed with saturated brine and then dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent; hexane / toluene = 9/1) to give 1.46 g (Y: 87.8%) of 4'-perfluorobutylbiphenyl-4-yl trifluoromethanesulfonate. Got it. The purity of the obtained compound was 99.8% as measured by GC.
    (13-e) Synthesis of the Polymerizable Compound 4'-Perfluorobutyl-4-vinylbiphenyl represented by Formula (213):
    First, in a 100 ml flask substituted with argon, 1.46 g of 4'-perfluorobutylbiphenyl-4-yl trifluoromethanesulfonate synthesized in the above (13-d), 1.10 g of tributylvinyl tin, tris ( Dibenzylideneacetone) (chloroform) dipalladium (0) 0.02 g, tri (2-furyl) phosphine 0.02 g, 2,6-di-tert-butyl-p-cresol 0.06 g, lithium chloride 0.36 g and dehydrated 20 ml of N-methylpyrrolidone was charged and stirred at 50 ° C. for 8 hours. After the reaction was completed, saturated aqueous potassium fluoride solution and ether were added to the reaction solution, and stirred for 1 hour. Insoluble matters were separated by filtration and the organic layer was separated from the filtrate. Thereafter, the organic layer was washed with 5% ammonia water, further washed with saturated brine, and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to obtain 0.74 g (Y: 66.2%) of 4'-perfluorobutyl-4-vinylbiphenyl. The purity of the obtained compound was 99.9% as determined by HPLC, and was found to be one point as measured by TLC. The phase transition temperature of the compound was as follows:
    IR measurement results and mass spectrometry confirmed the molecular ion peak at 398 and considering the raw materials used, it was confirmed that the resulting material was the compound represented by the formula (213).
    Synthesis Example 14 Synthesis of Compound 4 '[2- (perfluorobutyl) ethyloxy] -4-vinylbiphenyl represented by the following Formula (214):
    (14-a) Synthesis of Compound 2- (perfluorobutyl) ethyl trifluoromethanesulfonate represented by the following formula:
    First, 26.4 g of 2- (perfluorobutyl) ethanol and 75 ml of dehydrated methylene chloride were charged to a 200 ml flask equipped with a calcium chloride tube, and cooled to 5 ° C. Thereafter, 35.27 g of trifluoromethanesulfonic anhydride was added dropwise to the mixture under stirring. 12.65 g of triethylamine was then added dropwise to the mixture under stirring. After completion of dropping, the mixture was stirred for 24 hours. The reaction solution was washed with 30 ml of water, further washed with 30 ml of 3% sulfuric acid, then washed again with 30 ml of water, and dried over sodium sulfate. The solvent is then evaporated. The residue (boiling point 88 to 90 ° C./28 mmHg) was distilled off to obtain 35.26 g (Y: 91.8%) of 2- (perfluorobutyl) ethyl trifluoromethanesulfonate. The purity of the obtained compound was 94.2% as measured by GC.
    (14-b) Synthesis of Compound 4-hydroxy-4 '-[2- (perfluorobutyl) ethyloxy] biphenyl represented by the following formula:
    First, 3.0 g of 60% sodium hydride and 120 ml of dehydrated dimethoxyethane were charged into a 300 ml flask substituted with argon. Thereafter, 9.93 g of 4,4'-dihydroxybiphenyl was added while cooling and further stirred at room temperature for 2 hours. The reaction solution was again cooled to -60 ° C and 28.7 g of 2- (perfluorobutyl) ethyl trifluoromethanesulfonate was added dropwise to the reaction solution. The reaction solution was raised to room temperature and then stirred for 12 hours. After completion of the reaction, dilute hydrochloric acid and benzene were added to the reaction solution to separate the organic layer. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: benzene / ethyl acetate 9/1), recrystallized from toluene, 6.26 g of 4-hydroxy-4 '-[2- (perfluorobutyl) ethyloxy] biphenyl (Y: 27.1%). The purity of the obtained compound was 98.4% as measured by GC.
    (14-c) Synthesis of Compound 4 '-[2- (perfluorobutyl) ethyloxy] biphenyl-4-yl represented by the following formula:
    First, 5.00 g of 4-hydroxy-4 '-[2- (perfluorobutyl) ethyloxy] biphenyl synthesized in the above (14-b) and 100 ml of pyridine were charged into a 200 ml flask equipped with calcium chloride. Furthermore, it cooled to -20 degreeC. Thereafter, 3.92 g of trifluoromethanesulfonic anhydride was added dropwise to the mixture under stirring. After completion of the dropwise addition, the resulting mixture was stirred at 0 ° C. for 24 hours. The reaction solution was poured into water and extracted with ether. The ether layer was washed with 5% hydrochloric acid, further washed with saturated brine, and then dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/4) to give 4 '-[2- (perfluorobutyl) ethyloxy] biphenyl-4-yl trifluoromethanesulfonate 6.00 g (Y: 91.9%) was obtained. The purity of the obtained compound was 100.0% as measured by GC.
    (14-d) Synthesis of Polymerizable Compound 4 '-[2- (perfluorobutyl) ethyloxy] -4-vinylbiphenyl represented by Formula (214):
    First, 6.00 g of 4 '-[2- (perfluorobutyl) ethyloxy] -4-yl trifluoromethanesulfonate synthesized in (14-c) above in a 100 ml flask substituted with argon, tributylvinyl 4.04 g of tin, tris (dibenzylideneacetone) (chloroform) dipalladium (0) 0.11 g, tri (2-furyl) phosphine 0.05 g, 2,6-di-tert-butyl-p-cresol 0.23 g, chloride 1.35 g of lithium and 60 ml of dehydrated N-methylpyrrolidone were charged and stirred at 50 ° C. for 8 hours. After the reaction was completed, saturated aqueous potassium fluoride solution and ether were added to the reaction solution, and stirred for 1 hour. Thereafter, the insolubles were separated by filtration and the organic layer was separated from the filtrate. Thereafter, the organic layer was washed with 5% ammonia water, further washed with saturated brine, and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane / benzene = 9/1) and recrystallized from acetone to give 2.72 g of 4 '-[2- (perfluorobutyl) ethyloxy] -4-vinylbiphenyl. (Y: 57.8%). The purity of the obtained compound was 100.0% as determined by GC, 99.1% as measured by HPLC, and was found to be 1 point as measured by TLC. The phase transition temperature of this compound was as follows:
    IR measurement results and mass spectrometry confirmed the molecular ion peak at 442 and, considering the raw materials used, it was confirmed that the resulting material was the compound represented by the formula (214).
    Synthesis Example 15 Synthesis of Compound (R) -4- (1-methylheptyloxy) -4′-vinylbiphenyl represented by the following Formula (215):
    (15-a) Synthesis of Compound (R) -4 '-(1-methylheptyloxy) biphenyl-4-yl trifluoromethanesulfonate represented by the following formula:
    First, 5.00 g of (R) -4 '-(1-methylheptyloxy) -4-hydroxybiphenyl and 25 ml of pyridi were charged into a 100 ml flask equipped with a calcium chloride tube, and cooled to -20 ° C. . Then, 5.25 g of trifluoromethanesulfonic anhydrides were dripped at this mixture, stirring. After completion of dropping, the mixture was stirred at 0 ° C. for 24 hours. The reaction solution was poured into water and extracted with ether. The ether layer was washed with 5% hydrochloric acid, further washed with saturated brine and then dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) to obtain 7.04 g of 4 '-(1-methylheptyloxy) biphenyl-4-yl trifluoromethanesulfonate. The purity of the obtained compound was 99.5%, as measured by GC.
    (15-b) Synthesis of Compound (R) -4- (1-methylheptyloxy) -4'-vinylbiphenyl represented by Chemical Formula (215)
    First, 7.04 g of (R) -4 '-(1-methylheptyloxy) biphenyl-4-yl trifluoromethanesulfonate synthesized in the above (15-a) in a 100 ml flask substituted with argon, tributyl 6.22 g of vinyl tin, tris (dibenzylideneacetone) (chloroform) dipalladium (0) 0.17 g, 0.15 g of tri (2-furyl) phosphine, 2.08 g of lithium chloride and 2,6-di-tert-butyl-p- Several pieces of cresol crystals and 33 ml of dehydrated N-methylpyrrolidone were charged and stirred at 50 ° C. for 5 hours. After the reaction was completed, saturated aqueous potassium fluoride solution and hexane were added to the reaction solution, and stirred for 1 hour. Insoluble matters were separated by filtration and the organic layer was separated from the filtrate. Thereafter, the organic layer was washed with 5% ammonia water, further washed with saturated brine, and dried over sodium sulfate. The solvent is then evaporated. The residue was purified by silica gel column chromatography (eluent: hexane) and recrystallized from hexane to give 3.30 g (Y: 65.2%) of (R) -4- (1-methylheptyloxy) -4'-vinylbiphenyl. Got it. The purity of the obtained compound was found to be 99.9% by GC, 100.0% by HPLC, and 1 point by TLC. Melting point was 80.6 degreeC.
    IR measurement results and mass spectrometry confirmed the molecular ion peak at 308 and, considering the raw materials used, confirmed that the resulting material was the compound represented by the formula (215).
    EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the liquid crystal display (LCD) apparatus which concerns on this invention is described.
    The LCD device 10 according to the present invention includes a pair of substrates 1 and 2 and a liquid crystal layer interposed between the substrates 1 and 2, as shown in Fig. 8A. The liquid crystal layer comprises a plurality of liquid crystal regions 8 substantially surrounded by a polymer wall 7 made of a photopolymerizable resin material. In this embodiment, the liquid crystal region 8 is substantially surrounded by the substrates 1, 2 and the polymer wall 7. The substrates 1 and 2 each have a transparent electrode (not shown) of a desired pattern on their surface around the liquid crystal layer. The liquid crystal molecules 9 in the liquid crystal region 3 are twist-oriented in axisymmetry. In this embodiment, the twist angle was set to about 90 degrees.
    In an embodiment of the invention, the LCD device 10 is in transparent form. In the case of a reflective LCD device, one substrate may be formed of an opaque substrate such as a semiconductor substrate.
    In this embodiment, one liquid crystal region is formed for each of the plurality of pixel regions. When the pixels have different pitches in the directions perpendicular to each other, a plurality of liquid crystal regions can be formed for each pixel region. Even in this case, the liquid crystal regions can be arranged regularly in space.
    Hereinafter, a manufacturing method of the LCD device 10 according to the present invention will be described.
    Examples 1 to 3: Fabrication of LCD Devices Using Polymerizable Compounds by Mask Pattern Exposure
    Two glass substrates 1, 2 of about 1.1 mm thickness are provided, which consist of ITO (a mixture of indium oxide and tin oxide) and have a transparent electrode having a thickness of 50 nm. The glass substrates 1 and 2 were bonded while maintaining the gap therebetween as a cell thickness by a spacer (not shown) having a diameter of about 5 mu m to form a liquid crystal cell.
    On the liquid crystal cell, the photomask 20 which has the light shielding area | region 20a and the transmission area | region 20b shown in FIG. 9 was arrange | positioned. The precursor mixture was injected into the cell by capillary injection. The precursor mixture was obtained by uniformly mixing a polymerizable resin material, a liquid crystal material and a photoinitiator. As the polymerizable resin material, a mixture of 0.65 g of isobornyl acrylate, 0.15 g of 1,4-butanediol acrylate and 0.20 g of the polymerizable compound X shown in Table 1 below was used. 13.3 g of ZLI-4792 (Merck: Δn = 0.094) was used as the liquid crystal material. As the polymerization initiator, 0.04 g of Irgacure 651 was used.
    Polymerizable Compound XExample number One 2 3
    Thereafter, while applying a voltage having an amplitude of 3 V between the transparent electrodes, the liquid crystal cell was irradiated for 8 minutes at 100 ° C. with ultraviolet rays of the high-pressure mercury lamp through the photomask 20. The cell was placed under a 10 mW / cm 2 mercury lamp to obtain parallel rays. Thus, the precursor mixture in the cell was irradiated with ultraviolet rays having a spatially regular pattern of intensity distribution. The light irradiation temperature is preferably equal to or higher than the commercialization temperature of the mixture and is equal to or lower than the TN-1 point of the liquid crystal phase after phase separation. While the liquid crystal phase is formed by photopolymerization-induced phase separation, the orientation of the liquid crystal molecules is stabilized by applying a voltage to the liquid crystal phase.
    Subsequently, with the voltage applied, the cell was gradually cooled (10 ° C / hour) to 25 ° C (liquid crystal nematic state) and irradiated with ultraviolet light to the entire surface continuously without a mask for 3 minutes, The resin in the resin is further cured.
    The obtained liquid crystal panel was observed with a polarization microscope and as shown in FIG. 10, it was confirmed that it had a polymer wall 7 and a liquid crystal region 8 substantially reflecting the pattern of the photomask 20. It was confirmed that the radial quenching pattern 5 observed in the liquid crystal region 8 was oriented in the axisymmetric image with respect to the shaft near the center of the liquid crystal region 8. In this axisymmetric orientation, liquid crystal molecules having a molecular axis parallel to the polarization axis of the polarizing plate and liquid crystal molecules having a molecular axis inclined with respect to the polarization axis of the polarizing plate are continuously present. As a result, a radial quenching pattern was observed.
    Next, the polarizing plates were arranged on the outer surfaces of both sides of the liquid crystal panel such that their polarization axes were perpendicular to each other.
    The characteristics of the LCD device of Example 1 and Example 2 are shown in Table 2 below.
    In addition, evaluation conditions of an LCD device are as follows.
    Electro-optical characteristics: The voltage-to-transmission characteristic was measured using the liquid crystal characteristic evaluation system LCD-5000 (made by Otsuka Denshi Co., Ltd.). For reference, in a parallel-Nicole arrangement, a cell having polarizing plates on both sides of the glass substrate described above was used.
    Response time (response rate): The time required for changing the relative transmittance to 90% by varying the applied voltage between 0 and 5 V was measured. The sum of the time (ms) required to increase the transmittance and the time τ d (ms) required to decrease the transmittance was evaluated as τ r + τ d (ms).
    The T NI temperature in the liquid crystal region was observed with a polarizing microscope while the panel was heated at a rate of 0.1 ° C./min, and the temperature at which the isotropic liquid phase was observed as the nematic phase was measured at the measurement point in the center of the panel. The T NI temperature distribution in the liquid crystal region is expressed as the absolute value of the T NI temperature difference at the inlet and the peak facing the inlet.
    Voltage retention: After applying a selected pulse width of 10 seconds, a pulse voltage of 5 V in amplitude, the ratio of the voltage held in 16.7 ms was measured. The measurement temperature was 60 degreeC.
    Residual DC Voltage: DC 10V was applied for 1 hour by capacitor dielectric absorption and shorted for 1 second. After 10 minutes, the voltage value was measured. The measurement temperature was 60 degreeC.
    Panel residual image: The fixed pattern was shown on the liquid crystal panel at 60 degreeC for 1 hour, and voltage was removed (short-circuited) and the degree of panel residual image was observed.
    Example numberOne24578Comparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4 Transmittance (%) in black display1.20.90.60.70.30.20.72.20.60.6 Inversion phenomenon in gray-scale display * 1) ○○○○○○×△○○ Response rate (10 V; ms)58565053515334330220240 Pixel T NI Temperature (℃)78798080858783797675 Voltage retention rate (%)95969695959598939494 Residual DC Voltage (mV)100804565507065180330250 Panel persistence * 2) bbababbcdc
    Note: * 1) In the reversal evaluation, a symbol ○ indicates a state in which an inversion phenomenon hardly occurs, a symbol x indicates a state in which an inversion phenomenon is easily observed, and a symbol △ indicates a state in which an inversion phenomenon is barely observed. .
    * 2) In the afterimage evaluation, the levels (a) to (d) are respectively (a) the level at which no afterimage is observed, (b) the level at which the afterimage is observed in a very small amount (after 30 seconds, the afterimage pattern disappears), (c) The level at which afterimages are observed (afterimage pattern disappears within several minutes), and (d) the level at which afterimages are reliably observed (after several minutes, afterimage patterns are observed).
    As seen from Table 2, in the LCD devices of Examples 1 and 2, no inverted shape was observed. This reversal phenomenon was observed in the LCD devices of Comparative Examples 1 and 2 described later. In Examples 1 and 2, no increase in transmittance was observed in the direction of the large viewing angle. In Examples 1 and 2, no unevenness of any markings was also observed in the gray-scale markings.
    The response speed, residual DC voltage, and panel afterimage evaluation were relatively good as compared with Comparative Examples 2 to 4 described later.
    In the LCD apparatuses of Examples 2 and 3, the occurrence of disclination in the liquid crystal region was completely suppressed. In the LCD device of Example 1, a very small amount of declining occurred.
    Examples 4 to 6: Production of LCD Devices Using Polymerizable Compounds by Insulator Pattern Exposure
    In Examples 4 to 6, the LCD device was operated in the same manner as in Examples 1 to 3, except that the patterning wall was formed in the region of the liquid crystal layer in which the polymer wall was formed, and the ultraviolet rays were irradiated without using a photomask. Was prepared.
    Two glass substrates were provided, each having a thickness of about 1.1 mm and having a transparent electrode composed of ITO. As shown in Fig. 11, on one substrate, a patterning wall 42 containing a spacer 41 having a diameter of about 5 mu m was formed to a height of 2.7 mu m. In this embodiment, the patterning wall 42 was formed of negative photoresist OMR 83 (manufactured by Tokyo Corporation). Two glass substrates were bonded by sealing resin. As a result, a liquid crystal cell was produced.
    The precursor mixture was injected into the cell by vacuum injection. The precursor mixture was obtained by uniformly mixing a photopolymerizable resin material, a liquid crystal material, and a photoinitiator. As the photopolymerizable resin material, a mixture of 0.65 g of isobornyl acrylate, 0.15 g of neopentyl diacrylate and 0.20 g of the polymerizable compound shown in Table 3 below was used. 13.3 g of ZLI-4792 (Merck: Δn = 0.094) was used as the liquid crystal material. As photoinitiator, 0.04 g of Irgacure 651 was used.
    Polymerizable Compound YExample number 4 5 6
    After adjusting the orientation of the liquid crystal molecules by phase separation, the liquid crystal molecules were oriented in the axisymmetric state in the liquid crystal regions respectively surrounded by the patterning wall 42. For 15 minutes at room temperature, the precursor mixture in the cell was irradiated with ultraviolet under a high pressure mercury lamp of 6 mW / cm 2 . In order to completely cure the resin, ultraviolet rays were irradiated continuously for 10 minutes using the same lamp as the light source.
    By observing the obtained liquid crystal cell with a polarizing microscope, it was confirmed that liquid crystal molecules are oriented in the same symmetrical state as in Examples 1 to 3. This was confirmed in the following manner. The produced liquid crystal panel was rotated while fixing two polarizing plates whose polarization axes were orthogonal to each other. While the polymer walls are rotating, if the schlieren pattern of the liquid crystal region is constant, the axisymmetric orientation of the liquid crystal molecules is confirmed.
    Next, polarizing plates were arranged on both sides of the liquid crystal panel such that their polarization axes were perpendicular to each other. The characteristics of the LCD devices obtained in Examples 4 and 5 are shown in Table 2 above.
    As can be seen from Table 2 above, no reversal phenomenon was observed in the LCD devices of Examples 4 and 5. This inversion phenomenon was observed in the LCD devices of Comparative Examples 1 and 2 described later. No increase in transmittance in the large viewing angle direction was observed in Examples 4 and 5. In Examples 4 and 5, no staining of the marks was observed in the gray-scale marks.
    In the evaluation of the response speed, residual DC voltage and panel persistence, the results were relatively good compared to Comparative Examples 2 to 4. In the black display, the display state was also relatively good compared to Comparative Examples 2 to 4.
    Examples 7 and 8
    In Examples 7 and 8, LCD devices were manufactured in the following manner.
    As shown in FIG. 12A, a transparent electrode 52 made of ITO was formed on the organic substrate 51. As shown in FIG. By the photolithography process using the photosensitive polyimide, columnar spacers 53 having a thickness of about 5.3 μm were formed on the glass substrate 51. As shown in Fig. 12B, spacers 53 are formed in regions corresponding to regions other than the pixel region. Next, a patterning wall 54 having a thickness of about 3 m was formed to surround the pixel region. The patterning wall 54 was formed with the negative photoresist OMR 83 (manufactured by Tokyo Corporation). Then, the liquid crystal aligning layer 55 was formed using JALS-204 (made by Japan Synthetic Rubber Co., Ltd.) so that the spacer 53 and the patterning wall 54 may be covered. Although not shown, the liquid crystal aligning layer of the same form was formed on the transparent electrode of the opposing glass substrate. Two glass substrates were bonded together to prepare a liquid crystal cell.
    The precursor mixture of the photopolymerizable resin material, the liquid crystal material, and the photoinitiator was injected into the cell by vacuum injection. As the liquid crystal material, Nn liquid crystal material (Δε: -3.5; Δn: 0.08, T N-1 : 90 ° C; cell gap: 5.4 mu m, which is set such that the twist angle is 90 DEG using a chiral agent; Is unique). As the photopolymerizable resin material, 0.8 wt% of the polymerizable compound Z shown in Table 4 below was used. As the photopolymerization initiator, 0.15% by weight of Irgacure 651 was used.
    Polymerizable Compound ZExample number 7 8
    After the injection, a voltage of 5 V was applied to orientate in the axisymmetric state. The region in which the liquid crystal molecules were aligned in the axisymmetric state had a central axis in the center of the pixel region, and was formed inside the patterning wall 54. Thereafter, while applying a high voltage of 0.5 V higher than the threshold voltage, ultraviolet irradiation of 6 mW / cm 2 at 365 nm for 10 minutes at room temperature was performed to cure the photopolymerizable resin in the mixture. As a result, the axisymmetric orientation of the liquid crystal region was stabilized.
    Next, it arrange | positioned so that the polarization axis of a polarizing plate may orthogonally cross on both sides of a liquid crystal panel. The characteristics of the LCD devices manufactured in Examples 7 and 8 are shown in Table 2 above.
    As can be seen from Table 2, no inversion was observed in the LCD apparatus of Examples 7 and 8. This inversion phenomenon was observed in the LCD devices of Comparative Examples 1 and 2 described later.
    The response speed, residual DC voltage, and panel residual afterimage were relatively good as compared with Comparative Examples 2 to 4 described later. The display state in the black display was also relatively good as compared with Comparative Examples 2-4.
    Comparative Example 1: TN-LCD
    Similarly to Example 1, a glass substrate each having a transparent electrode composed of ITO was provided. A polyimide insulating film AL 4552 was applied as the alignment film on each of the glass substrates and subjected to friction treatment with nylon cloth. The produced glass substrates were arranged so that the friction directions were perpendicular to each other, and were bonded together with a space having an average particle diameter of 5 mu m.
    A liquid crystal material ZLI-4792 (containing 0.3 wt% of S-811) similar to that used in Example 1 was injected into a prepared liquid crystal cell.
    Next, polarizing plates were disposed on both sides of the liquid crystal panel so as to be parallel to and perpendicular to the friction direction of the alignment film corresponding to the polarization axis of the polarizing plate. The characteristics of the manufactured LCD device were evaluated, and the results are shown in Table 2 above.
    As can be seen from Table 2, in the LCD device of Comparative Example 1, an inversion phenomenon was observed in the gray-scale display.
    Comparative Example 2
    The photomask 20 shown in FIG. 9 was placed on the liquid crystal cell prepared in Example 1. FIG. The precursor mixture was injected by capillary injection into the prepared cell. The precursor mixture was obtained by uniformly mixing a polymerizable resin material, a photoinitiator and a liquid crystal material. As the polymerizable resin material, a mixture of 0.75 g of stearyl acrylate, 0.15 g of 1,4-butanediol and 0.10 g of tert-butoxystyrene was used. As photoinitiator, 0.04 g of Irgacure 651 was used. 13.3 g of ZLI-4792 (Merck: Δn = 0.094) was used as the liquid crystal material.
    Thereafter, as in Example 1, while applying a voltage to the cell, the surface of the liquid crystal cell on which the photomask 20 was formed was irradiated with ultraviolet rays, and photopolymerization phase separation was performed.
    The polarizing plate was arrange | positioned so that the polarization axis of a polarizing plate may be orthogonally Nicole arranged on both sides of the said liquid crystal panel. The characteristics of the manufactured LCD device were evaluated, and the results are shown in Table 2 above.
    As can be seen from Table 2, in the LCD device of Comparative Example 2, an inversion phenomenon was observed in the gray-scale display. Since the phase separation of the liquid crystal material from the polymer is insufficient, it has been confirmed that some resin materials are mixed in the liquid crystal region. When the voltage was applied, declining occurred, so that display characteristics were insufficient. When a voltage of 10 V was applied, the transmittance was 2.2%. Since this value is large compared with the LCD device of Example 4, for example, the low transmittance is considered to be the main cause of the occurrence of the disclination line.
    Comparative Examples 3 and 4
    As in Example 4, a patterning wall 42 (negative photoresist OMR 83 manufactured by Toka Corporation) containing a spacer 41 having a diameter of 5 mu m was formed on one of the pair of substrates. The substrate and the other substrate were bonded to each other with a sealing resin therebetween to form a liquid crystal cell. The precursor mixture was injected into the cell prepared by vacuum injection under reduced pressure conditions. The precursor mixture was obtained by uniformly mixing a polymerizable resin material, a photoinitiator, and a liquid crystal material. As the polymerizable resin material, a mixture of 0.65 g of isobornyl acrylate, 0.15 g of neopentyldiacrylate, 0.10 g of p-methylstyrene and 0.10 g of the polymerizable compound shown in Table 5 below was used. As photoinitiator, 0.04 g of Irgacure 651 was used. 13.3 g of ZLI-4792 (Merck: Δn = 0.094) was used as the liquid crystal material.
    Thereafter, as in Example 4, while applying a voltage to the cell, ultraviolet light was irradiated to the liquid crystal cell to advance the photopolymerization phase separation.
    The polarizing plate was arrange | positioned so that the polarization axis of a polarizing plate may be orthogonal Nicols arranged on both sides of the said liquid crystal cell. The characteristics of the manufactured LCD device were evaluated, and the results are shown in Table 2 above.
    As can be seen from Table 2, in the LCD devices of Comparative Examples 3 and 4, when observed with a polarization microscope, it was observed that the generation of the disclination line was suppressed when the voltage was applied. This is because a polymerizable compound having a liquid crystal like structure exists in the molecule in the polymerizable resin material. As a result, the light transmittance was 0.6% in the black display, showing a relatively good black display state.
    However, comparing the LCD devices of Comparative Examples 3 and 4 with Examples 1 to 8, the characteristics including the response speed (τ r + τ d ), residual DC voltage, and panel afterimage evaluation were insufficient. That is, the LCD device using the polymerizable compound according to the present invention is superior to the device of the comparative example, and means that the problem of the conventional LCD device can be minimized and solved by using the polymerizable compound according to the present invention.
    Example 9: TN Mode
    Fig. 13 is a sectional view of the LCD device 60 of Embodiment 4 according to the present invention.
    The LCD device 60 is almost the same as the LCD device of Example 1 except that the liquid crystal molecules 9 in the liquid crystal region are oriented in the TN state. In order to obtain the TN alignment, alignment films 61b and 62b were provided on organic substrates 61 and 62 in the vicinity of the liquid crystal layer disposed between the substrates 61 and 62, respectively. The alignment films 61b and 62b were subjected to friction treatment in a predetermined direction.
    The LCD device 60 was manufactured as follows.
    Glass substrates 61 and 62 each having transparent electrodes 61a and 62b made of ITO were provided. Liquid crystal aligning film AL 4552 (made by Japan Synthetic Rubber Co., Ltd.) was apply | coated on each glass substrate 61 and 62, and it was friction-processed with nylon cloth. Two glass substrates 61 and 62 having an alignment film were bonded to each other so that the friction directions were perpendicular to each other to prepare a liquid crystal cell.
    The same precursor mixture of photopolymerizable resin material, photoinitiator and liquid crystal material as used in Example 4 was injected into the cell by vacuum injection. ZLI-4792 (manufactured by Merck Co., Ltd.) was used as the liquid crystal material controlled to have a chiral pitch of 80 µm in this example.
    The photomask 20 having the light shielding region 20a and the light transmitting region 20b is disposed on the manufactured liquid crystal cell, and the liquid crystal region 8 surrounded by the polymer wall 7 in the same manner as in Example 1, respectively. To prepare a liquid crystal panel of the TN mode.
    Next, polarizing plates were disposed on both sides of the liquid crystal panel such that the polarization axes of the polarizing plates were parallel to and perpendicular to the friction direction of the corresponding alignment film. As a result, the LCD device 60 was obtained.
    In the LCD device 60, the liquid crystal molecules 9 in each liquid crystal region 8 were uniformly aligned in the TN state. The display characteristics did not change even when the display surface was pressed with a pen.
    When the polymeric compound which concerns on this invention is used, it was confirmed that the orientation stability of a liquid crystal layer and the uniformity of liquid crystal molecular orientation improve. As a result, display characteristics of the LCD device have been reinforced.
    In addition, the above-described effects can be obtained by LCD devices of display modes such as STN mode, SSFLC mode and ECB mode, which adjust the uniform orientation of liquid crystal molecules in various ways.
    As described above, in an LCD device including a liquid crystal layer having a liquid crystal region surrounded by a polymer wall or wall structure, a specific polymerizable compound may be used. The polymerizable compound contained a mesogenic group having a structure similar to that of the liquid crystal compound and a polymerizable functional group of styrene or -methylstyrene bonded to each other. By using such a polymerizable compound, the liquid crystal molecular orientation could be stabilized and the generation of the declining line could be suppressed. In addition, the interaction of the liquid crystal molecules and the polymer layer interface could be adjusted. This can minimize not only the problems caused by a decrease in response speed, a threshold characteristic of voltage vs. transmittance characteristics, a decrease in rapidity, etc., but also minimizing printing afterimages caused by an excessively strong memory effect at the interface.
    权利要求:
    Claims (14)
    [1" claim-type="Currently amended] A polymeric compound represented by following General formula (101):
    (101)
    In the food,
    R is H, R ', R'O, R'COO or R'OCO;
    R 'is a straight or branched alkyl or alkenyl group having 1 to 15 carbon atoms;
    A 1 and A 2 are independently a cyclohexane ring or a benzene ring which may include a substituent represented by the following general formula (102);
    X is H or CH 3 ; In addition
    Y 1 , Y 2 , Y 3 and Y 4 are independently H, F, Cl, CH 3 , CH 3 O, CF 3 or CF 3 O, wherein two of Y 1 , Y 2 , Y 3 and Y 4 The above is H, and when A 1 and A 2 are both cyclohexane rings, at least one of Y 1 , Y 2 , Y 3 and Y 4 is not H;
    (102)
    Wherein Y 5 , Y 6 , Y 7 and Y 8 are independently H, F, Cl, CH 3 , CH 3 O, CF 3 or CF 3 O, and Y 5 , Y 6 , Y 7 and Y 8 Two or more are H.
    [2" claim-type="Currently amended] The polymerizable compound according to claim 1, wherein in formula (101), A 1 is a cyclohexane ring and A 2 is a benzene ring.
    [3" claim-type="Currently amended] The polymerizable compound according to claim 1, wherein in Formula (101), A 1 and A 2 are cyclohexane rings.
    [4" claim-type="Currently amended] A polymerizable resin composition comprising a polymerizable resin material containing the polymerizable compound according to claim 1 and a photoinitiator mixed with each other.
    [5" claim-type="Currently amended] A polymeric compound represented by the following general formula (103):
    (103)
    In the food,
    R is a straight or branched chain alkyl or alkoxy group having 1 to 15 carbon atoms where H, F or any hydrogen atom may be substituted by a fluorine atom;
    Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 are independently H or F;
    X is H or CH 3 ;
    At least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 is F, provided that R is a straight chain alkyl group in which any hydrogen atom is unsubstituted by a fluorine atom.
    [6" claim-type="Currently amended] Cured polymer obtained by superposing | polymerizing the polymeric resin composition of Claim 4.
    [7" claim-type="Currently amended] A liquid crystal display device comprising a polymer wall interposed between a pair of substrates and a liquid crystal region surrounded by a polymer wall, said polymer wall comprising a cured polymer according to claim 6.
    [8" claim-type="Currently amended] 8. The liquid crystal display device according to claim 7, wherein the polymerizable resin composition comprises a polymerizable compound in an amount of about 3 wt% or more and about 40 wt% or less.
    [9" claim-type="Currently amended] A liquid crystal display comprising a polymer wall interposed between a pair of substrates and a liquid crystal region surrounded by a polymer wall, wherein at least a part of the region of the polymer wall in contact with the liquid crystal region comprises the cured polymer according to claim 6. Device.
    [10" claim-type="Currently amended] The liquid crystal display of claim 7, wherein liquid crystal molecules in each of the liquid crystal regions are aligned in an axisymmetric state.
    [11" claim-type="Currently amended] The liquid crystal display of claim 7, wherein the liquid crystal regions are regularly aligned.
    [12" claim-type="Currently amended] 8. The liquid crystal display device according to claim 7, further comprising a liquid crystal alignment film disposed on a surface of at least one pair of substrates in contact with the liquid crystal region.
    [13" claim-type="Currently amended] 8. The liquid crystal display device according to claim 7, wherein the liquid crystal molecules of the liquid crystal region are oriented in one of a twist nematic type, a super twisted nematic type, a field controlled birefringence type and a surface stabilized ferroelectric liquid crystal type.
    [14" claim-type="Currently amended] 8. The liquid crystal display device according to claim 7, wherein the liquid crystal regions are each provided for one pixel region which is a minimum unit for display.
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    同族专利:
    公开号 | 公开日
    JP3807576B2|2006-08-09|
    US6388146B1|2002-05-14|
    JPH11217342A|1999-08-10|
    KR100318400B1|2001-12-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-01-28|Priority to JP01620998A
    1998-01-28|Priority to JP10-016209
    1999-01-28|Application filed by 마찌다 가쯔히꼬, 샤프 가부시키가이샤, 노자와 순따로, 간또 가가꾸 가부시끼가이샤
    1999-08-25|Publication of KR19990068186A
    2001-12-22|Application granted
    2001-12-22|Publication of KR100318400B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP01620998A|JP3807576B2|1998-01-28|1998-01-28|Polymerizable compound, polymerizable resin material composition, polymerized cured product, and liquid crystal display device|
    JP10-016209|1998-01-28|
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