TW201217501A - Liquid crystal composition and liquid crystal device - Google Patents

Abstract

This invention provides a liquid crystal display device with improved burn-in property and pretilt angle stability. A liquid crystal display device according to this invention has a construction wherein a liquid crystal layer that can be driven by applying a voltage is sandwiched between a pair of voltage-applicable substrates on which voltage for controlling cell gap may be applied. The liquid crystal layer comprises liquid crystal composition (A) formed by one or more than two kinds of liquid crystal molecules, and polymerizable compound (B) including hardened material, for controlling the tilt of the liquid crystal molecules, that is formed by polymerizing one or more than two kinds of polymerizable compounds using energy line or heat or their combination. Among the polymerizable compounds, at least one kind of polymerizable compound includes, within its molecule, two or more than three polymerizable functional groups, and the two or more than three polymerizable functional groups include more than two different polymerizable functional groups.

Description

201217501 VI. Description of the Invention: 1. Field of the Invention The present invention relates to a liquid crystal display element having a pair of substrates capable of applying a voltage by controlling a gap of a liquid crystal cell, and clamping can be performed by applying an applied voltage: The structure of the liquid crystal layer 'and the crystal layer contains a hardened material which is polymerized by a combination of energy rays or heat or a combination of materials to control the inclination of the liquid crystal molecules. [Prior Art] A liquid crystal display device of a PSA (Polymer Sustained Alignment) type is a cured product in which a polymerizable compound is polymerized in a liquid crystal cell for controlling the inclination of a crystal molecule, and because of its rapid reactivity and high contrast, Therefore, it is expected to be the next generation of liquid crystal display elements. The cured product is controlled in a state with respect to the liquid crystal cell to control the liquid crystal molecules to a certain inclination. In the state in which the polymerizable liquid crystal composition of the liquid crystal compound and the polymerizable compound is placed on the substrate in a state in which the voltage is applied to the sub-orientation in the state of being oriented, the polymer is irradiated with ultraviolet rays or the like. Oralized sigma polymerization, and the hardened matter memorizes the orientation state of the liquid crystal. The problem of the gentleman's paint component is that the same pattern is continuously displayed for a long time. The reason for the branding is not the simple cause of the compound, and (2) the change in the inclination of the initial valence of the residual (four) polymerization (change in the pretilt angle). In order to solve the problem of (1), the polymerization of the polymerizable compound is promoted, and all of the i = i is to promote the progress of the polymerization, and the addition of the polymerization initiator is effective. In the polymerizable liquid crystal composition, in order to increase the residual amount of the polymerizable compound, the polymerization initiator in the liquid crystal display element and the voltage retention rate of the 70-decomposition are reduced to become a new brand. because. If the initiator is used, the polymerization will not proceed at all, and the branding caused by the 201217501 compound cannot be avoided. In order to solve the problem (2) ’ II, it is effective to promote a polymerization by giving a large amount of energy during the polymerization time, gUg, strong ultraviolet rays, and the like. In this method, the polymerizable compound can be completely cured by the addition amount of a small amount of the polymerization initiator, and the residue of the compound can be suppressed. However, in this method +, the manufacturing apparatus inevitably causes a decrease in manufacturing efficiency, and a new problem such as deterioration of the liquid crystalline compound 4 due to ultraviolet rays is generated. Therefore, in the liquid crystal composition containing a polymerizable compound, it is difficult to reduce the amount of the unpolymerized polymerizable compound which remains for a long time and the residual (four) combination. This requires a non-polymerized yarn _ a liquid crystal composition containing #polymerizable & The 'production of the brand' is also known to be caused by a change in the pretilt angle of the liquid crystal molecules in the silk-containing compound, the attack, and the composition. In particular, if the polymer (4) of the hardened compound of the coincident compound is soft, it is composed; in the case of 6 elements, the structure of the polymer will change to t: The inclination changes. Since the change in the pretilt angle greatly affects the speed, it is the cause of the branding. Therefore, in order to solve (3), it is effective to form a polymerizable compound which does not change the structure of the t-structure. Further, the (four)-complex compound for a liquid crystal display element is known, and a biphenyl skeleton is known as a reference patent document. However, the polyfunctional acrylate compound may be polymerized in the ageing period in which it is hardened by the use of a sealant or the like. In addition, since the solubility of the liquid crystal molecules is low, there is a problem in that the polymerizable compound is precipitated when the polymerization is carried out to attack BH, and the composition is injected into the liquid crystal cell. ΐ, compared with the acrylic acid vinegar compound, the polyfunctional methacrylic acid compound has a qualitative improvement of the 'but the polymerization rate is low, and the unpolymerized polymerizable zygote #other-side' has been revealed - in order to improve the solubility A polymerizable compound having a ratio of 4 to 4 (see Patent Document 2). Although the compound phase discotic compound has an improvement in solubility, since a spacer is interposed between a ring-junction and a difficult-to-δ functional group, the rigidity of the molecule is lowered, and 201217501 controls the tilt of the liquid crystal molecule. Decrease in ability. In addition, there are problems with this compound surface. When the ability to control the tilt of the liquid crystal molecules is low, g is not uniform and becomes a cause of display defects. For example, the liquid crystal display element using the conventional polymerizable liquid crystal composition is difficult to satisfy the stability of the imprinting property and the pretilt angle. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-307720 (Patent Document 2) pct International Patent Publication No. WO 〇 〇〇 / / / / 【 发明 发明 发明 发明 发明 发明 发明Problem to be Solved The problem of the present invention is to provide a feature indicating the solubility of the polymerized heterocrystal composition, and to improve the surface (10). [Technical means for solving the problem] The liquid crystal display element has a liquid crystal layer J which is driven by an applied voltage by controlling the liquid crystal cell between the liquid crystal cells, and is sandwiched between the liquid crystal cells. One or two or more kinds of liquid crystals composed of liquid crystals and composed of (A), U and coffee energy or heat, or a combination of fresh, controlled liquid crystals in which two or more kinds of polymerizable compounds are polymerized At least one type of riding compound (B) having a gradient of molecular inclination, the polymerizable opening () having two or more polymerizable bureaucratic groups in the knife, and two or more The polymerizable functional group is a two or more different functional groups. [Comparative to the effects of the prior art] It is possible to provide a liquid crystal display element which improves the display characteristics, and the stability of the branding characteristics and the pretilt angle is greatly improved as compared with the conventional liquid crystal display element. [Embodiment] A human liquid is used for a liquid crystal display element, which is small in a liquid crystal composition. & confers liquid crystal orientation ability, and controls the amount of transmitted light by utilizing the double 201217501 refraction of the liquid crystal composition. ) The night crystal display element is useful in AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), and STN-LCD (super twisted nematic liquid crystal display element). Particularly useful in LCDs, and especially suitable for VA-LCD (vertical directional liquid crystal display elements), 〇CB (〇pticqing Compensated Birefringence, · optically compensated birefringence) - LCD and - LCD (4K to electric field effect liquid crystal display element). Further, it can be used for a transmissive or reflective type liquid crystal display element. The two-wire plate of the liquid crystal cell used in the liquid crystal display element can be made of glass, or __, which can be used as a luminescent material, or alternatively, a material such as Shi Xi et al. can be used. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide pT on a glass plate #transparent substrate. Μ片和=如可# is formed by pigment dispersion method, printing method, electrodeposition method or Ϊ色ΐί。ί. A method for producing a color calender using a pigment dispersion method is disclosed in which a sap filter and a photo-curable composition for a light sheet are applied onto the transparent substrate, and the texture is heated or silked. Make it harden. This step is performed separately for the red and blue colors, and the halogen portion for the color filter and the light sheet can be prepared. The ruthenium electrode is provided with a TFT, a thin film diode, and a metal insulator metal resistor 71: a member of the temple active element. The substrate is placed in a relative orientation, and the transparent hybrid layer is made _. , the whole 3 = 1 = adjust the spacing of the ί plate. At this time, the thickness of the dimming layer to be obtained is adjusted to LL5^10μηΊ 〇, and the refractive index anisotropy Λη of the litter and the thickness of the cell are preferably maximized. Moreover, when there are two polarizing plates, the plate can be adjusted to the optimum angle of view and contrast. Further, a retardation film which expands the viewing angle by ^ can also be used. The spacer may, for example, be a plastic oxide wire or a photoresist material. Thereafter, the liquid crystal is provided with a % of the resin to be hardened (4) sealed and printed on the substrate. The substrates are bonded to each other and heated to thermally cure the sealant. On the substrate of the sea, a method of sandwiching the polymer-stabilized liquid crystal composition between the south and the violent plate can be carried out by vacuum injection or ODF. Further, 201217501 - a method of polymerizing a polymerizable compound, since it is desired to carry out the polymerization rapidly, it is preferable to use an active energy ray* such as an irradiation line or an electron beam to aggregate the polymerizable compound. When using ultraviolet light, a polarized light source or a light source can be used. Further, when the liquid crystal composition is sandwiched between the two substrates, at least the substrate on the irradiation surface side needs to have an appropriate lifetime for the active energy ray, and the liquid crystal or the electric field can be used to orient the liquid crystal. At the same time, it is also possible to use a mask in the case of light irradiation, and only after the specific portion is polymerized, the directional state of the unpolymerized portion is subjected to the irradiation of the active energy ray by changing conditions such as 吏, %% magnetic, or temperature. It is polymerized. In particular, in the case of ultraviolet light exposure, it is preferable to apply an alternating current to the liquid crystal composition of the trimeric compound while performing ultraviolet light. The alternating current applied is preferably 2 to 1 frequency of the frequency leg, and more ideally, the alternating current is frequency to 1 (7)^hz, and the electric liquid shows the pretilt angle required by the component on the day 0. select. That is, the pretilt angle of the liquid crystal display element can be controlled by applying two. Regarding the liquid crystal display of the MVA mode, it is preferable to control the pretilt angle to 80 degrees to the viewpoint of orientation stability and contrast. The calorific value at the time of shooting is preferably in the temperature range in which the liquid crystal composition of the present invention can maintain the daily state of the liquid. The temperature near room temperature is most desirable, i.e., polymerization at a temperature of from 15 to 6 G °c. For the ultraviolet lamp, a gold 1 halogen lamp, a mercury lamp, an ultra high pressure mercury lamp, or the like can be used. Further, the ultraviolet ray to be irradiated is preferably an ultraviolet ray of an absorption wavelength-wavelength range of the non-audio-crystal composition, and it is preferably irradiated with ultraviolet rays as needed. =, the intensity of the external line of the shot, the ideal state is 0 lmW / cm2 ~ 1 〇〇 w / cm2, the state is 2mW 々 m2 ~ 80W / cm2. The energy of the ultraviolet ray irradiated can be tiankouzhou i, but the ideal state is 1 〇 to 1 〇 _mJ/cm 2 = 100 to 7000 mj/cm 2 . The intensity can also be changed when ultraviolet rays are irradiated. The time for illuminating the ray is appropriately selected depending on the intensity of the ultraviolet ray to be irradiated, but it is 10 to 600 seconds. Further, heat treatment is performed on the liquid crystal display element of the present invention obtained by polymerization in order to reduce the initial characteristic change and achieve stable characteristics. The heat treatment temperature of 201217501 is 50~25 (the range of TC [g', the heat treatment time is preferably in the range of 3Q seconds to 12 hours. For the polymerizable compound of the invention, it is necessary to control the liquid crystal material after polymerization = orientation Sexuality, and the length of the _ orientation state. Therefore, f is required to adjust the orientation of the liquid crystal and the surface strength of the cured product. Furthermore, since the polymerizable compound remains after hardening: a large amount of polymerization initiator remains, which may result in Since the defect is indicated, it is necessary to carry out the polymerization with a polymerization initiator having a small amount of i or a polymerization initiator. Further, the polymerizable compound may be a compound exhibiting liquid crystallinity or may not exhibit a compound. It is only possible to use a compound which is a monomer-forming monomer or a polymer-forming oligomer in the technical field. However, after the polymerizable compound is cured, the liquid crystal layer must be present. Liquid crystal _.g] When adding a non-polymerized residual crystal shim, it is necessary to adjust the amount of addition to exhibit liquid crystallinity. The compound is at least containing lanthanum, but _ wants to contain t The ideal type of cancer is one to three kinds. In addition, when the rate of polymerization is too small, the orientation restriction force with respect to the liquid crystal molecules will be weak, and the amount of polymerization will increase when it is too polymerized. The lower limit of the polymerizable compound remaining unpolymerized is preferably _ mass%, more preferably G.Q3 mass%, and the upper limit is preferably 2.0% by mass, more preferably 10% by mass. For the human and the compound, a single compound may be used, and two or more kinds of chemical compounds may be used. However, at least one of the polymerizable compounds (B) must be used. The polymerizable compound (B) has two in the molecule or When three or more sexual officials have two polymerizable functional groups in the molecule, two different functional groups are polymerized, and when the compound has three polymerizable functional groups, the polymerizable functional groups are three different functional groups. In the case of the compound of the group, the two functional groups are the same functional group, and the remaining one is a g-energy group. When there are four polymerizable functional groups, one polymerizable functional group is four different functional groups. The combination of 3 = 3 kinds of non-functional groups and 2 different officials The case of the energy base (packaged "has the same functional group and has a different functional group"; 201217501 kinds of polymerization, functional group 'which has 2 identical functional groups, and has ί ::; a case where two functional groups are sub-sub-different; and a total of two kinds of hydro-functional s-groups having two identical functional groups and having two functional groups different therefrom. In the case of a compound having five or more polymerizable functional groups, the following is the case where the polymerizable spheroidal filaments are as follows: the all-neighbors and the conjugated functional groups are different; Among the polymerizable functional groups of the polymerizable functional group, only two phases are the same. The ruthenium-based functional group is a functional group different from the two functional groups. * The polymerizable functional group in the polymerizable compound is preferably 2 to 6 in a preferred state, and more preferably 2 to 5 in a state of 2 to 4, and more preferably 2 to 4 in a state of 2 to 3. The most ideal form is two. Further, the type of the polymerizable functional group contained in the i-polymerizable compound is complicated and difficult to manufacture. Therefore, it is more ideal

There are three kinds of patterns to think about, and the most ideal ones are two. : H Further, when the number of polymerizable functional groups is 4 or more, the monomer layer% decreases the polymer layer_news, but the agglomeration of the silky polymer layer 'is disturbing the directionality of the liquid crystal. Therefore, the amount of addition used is limited. The conjugated compound (B) may be used singly or in the form of a mixture of 2 or more, or may be used by mixing other polymerizable functional groups. " The polymerizable compound (B) is mixed with another polymerizable compound to sufficiently achieve the effect of the polymerizable compound (9), and the polymerizable compound (8) and the polymerizable compound of the compound (8) are mixed with the polymerizable compound. The amount of the poly(1) compound (Β) is more than 5Q% by mass, and the sample is more than 7〇% by mass. The more ideal form is 8〇% by mass or more. % or more. Heart m ', the polymerizable compound is combined by ray or heat, or the combination of the lie to form a solid, but in each step up to the polymerization step, it must be well dissolved in the liquid crystal molecule When the liquid crystal molecules are low in solubility, the precipitation of the polymerizable compound is unevenly present in the liquid crystal display element, and the liquid crystal display element is not in the entire region, resulting in the capping method & 'The compatibility of the polymerizable compound with the liquid crystal molecule can be improved = It is desirable to improve the compatibility with the liquid crystal molecules, for example, the polymerizable compound is ideal for the left and right. The former crane has 1 jii liquid crystal in I. In addition, in the case of a polymerizable compound, the electrons are shifted by a large amount of electrons, so that the polymerized i-like substance in the above-mentioned part is in a molecular-symmetric ride, and the knot is lowered. The compatibility of the polymerizable compound with the liquid crystal composition is as follows: ^ This liquid hydrazine composition does not help to limit the orientation of the liquid crystal composition. Eight of you ^ * hunting is improved by the use of liquid crystal composition The polymerization is such that when the concentration of the hardened material in the hard portion of the liquid crystal display element is uniformly distributed throughout the entire area of the liquid crystal display element, the angle of the cured material is not obtained, and the display defect is still caused. In the case of the pre-dip, the polymerization rate of the polymerizable compound in the polymerization step, the time is not long: the production efficiency is low, and the defects are deteriorated due to the long-term denier, and defects are generated. The use of poly: ϊϊ 的 的 , , , , 留 留 留 留 留 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用Want to achieve the most suitable polymerization rate For an appropriately selected in this case, the polymerizable group 201,217,501 'also "polymerizable group in the molecule ⑽ system - into a suitable polymeric # County. However, it is difficult to find a single-and polymerizable group having an optimum polymerization rate. Therefore, it is preferable to increase the polymerization rate (IV) of the polymerizable functional group and the polymerizable functional group f having a slow polymerization rate to the intramolecular polymerization rate. According to the molecular weight of the hardened material in the foregoing element, the gambling is good, and the display defect of the liquid crystal display element can be solved. The liquid crystal display element has a liquid crystal layer formed of a composition containing a ruthenium liquid crystal and a cured product. Before the polymerization is carried out by using an energy ray or the like, the polymer compound containing the polymerizable compound (8) and the mixture of the liquid are sandwiched between the substrates. The polymerizable compound (9)' has two or more polymerizable groups in the molecule, except that the polymerizable functional group is all phase-molecular structure, and the polymerizability is ideal for the soil. ο~ (R—is) represents & polymerizable functional 〇(R^l) 0,

〇, Ο (R-2) CF.

.〇, oi, occr ο(R-l) 〇 ο (R-7) (R-3) ch3(R-8) (R-4) (R-5) H3c, h3c

(R-9); o*(R-10)

H3c o

Coo·

-SH (R-ll) (R-12) o(R-13) 01 (R14) Centrifugal fu functional group by *radical polymerization, self-supporting addition polymerization, yangfang, 3 and ionic polymerization harden . The system is to use the purple-killing polymerization as the poly-LrU, 仃 when the 'preferential state is the formula (R-υ, formula (R-2), formula (R-4), work, formula (R-7), (R-13) and male -15), more reasonable (R-15) 12 201217501 The situation is as follows (r-1), literacy-2), . (R-7), literacy-- The more ideal form of the formula (R - 13) is the formula (R-1) and the formula (R-2). Polymerizable compound (B) 'To increase the polymerization rate by UV irradiation, it is preferable to expand the conjugated system of π electrons in the molecule, and it is preferable that at least one pass is made in the molecule. The structure represented by the formula (Α-1)~(Α-4), ~ Υ11 γ12 n

(wherein, X11 to X30 represent a hydrogen atom, a halogen group, a cyano group, or a group or a base group which may be a straight chain or a ruthenium group having a number of anatomical atoms of 1 to 8, and a subgroup adjacent to the alkyl group. The group may be substituted by an oxygen atom, -C = C-, -OC-, -COO-, -CO-, -S-, and the hydrogen atom in the alkyl group may be substituted by a _ group.), more ideally, A more desirable configuration of the structure having the general formula (A-2) to (A-4) in the molecule is a structure having a general formula (A-3) and/or (A-4) in the molecule. Further, the polymerizable compound (B) is preferably a compound represented by the formula 1. A2-B2^-A3-(P2) 2 (I) p1 and p2 are polymerizable functional groups. When the ultraviolet polymerization is carried out as a polymerization method as described above, the preferred form is the formula (R-1) and the formula (( R-2), formula (R-4), formula (R-5), formula (R-.7), formula (R-11), formula (R-13) and formula (R_15), more ideal The state is the formula (R-1), the formula (R-2), the formula (R-7), the formula (R-ii), and the formula (13). The more ideal form is the formula (R-1) and (R-2). A1 and A3 are each independently 'representing 1,4—phenylene, benzene-1,3,5-triyl, benzene-1,3,4-triyl, benzene-1,3,4,5-tetrayl, 1,4 - Cyclohexyl, cyclohexane - trisyl, cyclohexane, 1,3,4 - triyl, cyclohexane - 1,3,4,5-tetrayl. Ratio 1 to 2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-2,5,6-triyl, naphthalene 13 201217501 _2,5,6,7 - tetrakis, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene - 2,5,6-triyl, 1,2,3, 4-tetrahydronaphthalene-2,5,6,7-tetrayl or 1,3-dioxanthene-2,5-yl-based, A and A are independent of each other, may not be substituted, or are numbered by bees a halogen group having a carbon number of 1 to 12, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen, a cyano group or a nitro group, Among them, 1,4 -phenylene, phenyl-, 3 5 -triyl, benzo-1,3,4-triyl, benzene-l, 3, which are unsubstituted or substituted by one or more halogens , 4,5—tetrayl, 1,4—cyclohexylene, cyclohexene-U, 5-triyl, cyclohexane-H4-triyl, cyclohexane-^^tetrayl, naphthalene-2,6 —diyl, naphthalene-2,5,6-triyl, naphthalene-2,5,6,7丄tetrayl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,2 , 3,4-tetrahydronaphthalene- 2,5,6-triazine, or 1,2,3乂-tetrahydronaphthalene- 2,5,6,7-tetrayl is preferred, — —phenyl, phenyl, phenyl-1,3,4-triyl, benzene, 3,4,5—tetrayl, ι, 4-cyclohexylene, cyclohexane-1,3,5 — Triyl, cyclohexane-triyl, cyclohexane-tetrayl, naphthalene-2,6-diyl, naphthalene-2,5,6-triyl, naphthalene-2,5,6,7-tetrayl The tetrahydronaphthalene 2,6-diyl group is more desirable. A2 represents 1,4—phenylene, ι,4—cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, nod- 2 , 5-diyl, '(2), ditetrahydronaphthalene-2,6-diyl or U-dioxane- 2,5-diyl, these groups may be unsubstituted or have 1 to 12 carbon atoms The base of the burning, the number of carbon atoms, 12, the stone ίί, the number of carbon atoms, 1~12, _ oxy, dentate, ideal, ... stretch phenyl, - stretch "= phase ϋϋ 3 提高 improve the use of ^ irradiation The degree of polymerization at the time, in comparison, the kebyl group, the oxygen group; the base = (di) re-aromatic = substituted 'and more desirable form is not taken ~ 4 of the burning group, the number of carbon atoms _ A halogenated alkane with a carbon number of 1 to 4, which has a _σ a = 7 butyl number of 14. The milk base is substituted by a methoxy group or a crypto-substituent, and more emphasis is placed on the solubility of the 14 201217501 The ideal state is a halogenated alkyl group of 1 to 4, a carbon atom, a sulfonium group, a slave atom, a methoxy group, or a sulfonyl group, and a carbon atom number of 1 to 4 is unsubstituted. In the case of improvement in mechanical strength, it is more reasonable and independent of B2. The pattern is ~----.-0CH factory, -c2h4-, -CH2〇-, -(10)-, -〇cJCH2, :cTcS: 'chCH2〇C〇°' ' -c—-- ^ ooc -co 〇C2h", -occ^3—C〇〇_, —〇〇C-CCH3=ch-, —or”—2H4---CAOCO——C2H4C00-,

And - 〇 CF2 -, according to the ease of manufacture and liquid crystal orientation, his point is more ideal - 〇---och2---ch2o___COO -> 〇CO_ > - η ττ _nntJ, one 〇 C - And a single button, particularly ideal form is to go 2 -, a CH2 〇 -, - c 〇〇 -, _oco - and single bond. When η is large, the compatibility with liquid crystal molecules will decrease. Therefore, it is more desirable that n is 〇~2, and 〇 and 1 are more desirable. More specifically, the compound represented by the formula (I) is preferably a compound represented by the following formula (I-1) to formula (Ι-40). 15 201217501

(Μ) (1-2) (1-3) (1-4) (1-5) (1-6) (1-7) (1-8) (1-9) (1-10) (1 -11) 0-12) (1-13) 16 201217501

(1-14) (1-15) CI-16) (1-17) (1-18) (1-19) (1-20) (1-21) (1-22) (1-23) ( 1-24) (1-25) 17 201217501

(1-26) (1-27) (1-28) (1-29) (1-30) (1-31) 18 201217501

(1-32) (1-33) (1-34) (1-35)

(1-36)

(1-37) 19 201217501

(1-38) (Γ-39)

In the liquid crystal composition containing a polymerizable compound of the present invention, at least one kind of polymerizable compound represented by the formula (I) is contained, and it is preferable that the liquid crystal composition represented by the formula (I) contains a quinone species of ~5 species. Kind ~ 3 species. When the S ratio of the compound represented by the formula (1) is too small, the orientation regulating force for the non-polymerizable liquid crystal compound is weak, and when it is late, the energy required for the polymerization is increased, and the polymer is not polymerized and remains. Since the amount of the polymerizable compound is increased, the lower limit value is preferably 001% by mass, more preferably 0.03% by mass, and the upper limit is preferably 2% by mass, more preferably. The state was 1.0% by mass. The liquid crystal molecules used in the present invention may be a compound which exhibits a liquid crystal phase alone, or a compound which exhibits a liquid crystal phase when two or more types are combined. When two or more types of liquid crystal molecules are mixed and used, they may be various combinations, but one type includes the formulas (Π), (ma), (mb), (IIIc), (iVa), (IVb), and The compound represented by (IVc) is preferred. In the compound represented by the formula (II), R21 and R22 are each independently, and preferably, the group is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (including the presence of the groups) One methylene group or two or more methylene groups which are not adjacent are substituted by ~〇20 201217501. One or two or more hydrogen atoms present in the group i are substituted with a ? atom or a helium atom.), more The ideal state is an alkoxy group having a number of carbon atoms i to $1 to 5, and a dilute oxy group having a carbon number of 2 to 5 to 6 to 6, particularly preferably a carbon atom number to 5 alkoxy groups having 1 to 5 subunits. The base or the slave M21 W2 and M23 are independent of each other, and the preferred form is an anti-fluorenyl group (including one CH2 group present in the group or two λ = atoms not adjacent), and a phenyl-phenylene group ( Containing one or two of the groups present in the group === substituted for (10), 3~l-Μ-phenyl, 3,5-difluoro-丨4, 1,4-cyclo ring Hexenyl, w-bicyclo[22.2]expersinyl, definite-μ-diyl, more ideally the form is trans-1,4-extended cyclohexyl, j,4' ring [2.2.2]exyl The particularly ideal form is anti-Μ-extension, and the pattern is 〇, i or 2'. The more ideal form is 3 / f and L are independent of each other. The ideal form is single bond, - , -〇CH2-, -ch2〇—, —0CF2—, —CF2〇:, — — or 〇TC—“The more ideal form is single bond, state i single; built or 'ckd,. H "or -CH2〇-, a more ideal view of the formation, structure, according to the chemical stability of the CH-CH-CH=CH---C=C«- and the structure, and sulfur and oxygen The structure of the atomic bond is also less than ideal for the structure of the knot, the structure of the bond between the nitrogen atom and the oxygen atom, and the structure of the sulfur atom bond of the nitrogen tube. In the above description, as a specific structure, it is represented by a group consisting of the following general formula (η-Α) to the general formula (ΙΙ-Ρ) ^^^^^^^^^^^

(II-A) (Ιί-Β) (INC) (H-D) (I[-E) (U-F) (II-G) r23~Ch〇h〇>-r24

(II-J) R24 OI-K) (U-L) r22_^^~^〇M〇)~r24 (U-l) (H_M) r?^0~(I)~〇--r24 (H-H)

(Π-Κ) 〇i-〇)

Oi-P) * (wherein 'R and R24 are each independently, and represent a carbon atom to (7), a 1G oxy group, a carbon liver 2 ^ 1G _ group or an alkoxy group having 3 to 10 carbon atoms; R and R24 are each independently a more desirable form of an alkane having a carbon number of 丄 to ι〇, an alkoxy group having a reverse number of 1 to 10 or an alkenyl group having 2 to 10 carbon atoms, more preferably The state is a carbon atom number of 丨 to 5 or a number of carbon atoms 〗 to 〗 〖. Alkoxy groups. - also A) to the compound represented by the formula (Π-P), preferably Ϊ22:-A), formula (n-B), formula (I1-C), formula-E ), a compound represented by the formula (I-formula (I1-K), more ideally tfT 1 ( } ' ^^(Π~〇) ' ' ^^(Π-Η)^Ι^ (Π I) is a compound represented by the formula (11), which contains at least one compound represented by the formula (11), which is more than one kind of one to ten kinds of 'more than ideal'. (1), the lower limit of the content of the compound _ compound is 5 mass 〇 'more desirable sorrow is 10 mass %, more ideal form is 2 〇 mass %, 22 201217501 especially ideal The sample H is % 胄 % > 32 ί Wei 'more ideal form is 7. The quality of autumn, = 2-15 or more methylene substitution is ▲ methylene or not adjacent 2 = ί_; Substituted as ^ atom - base ΐ carbon atom cleavage, the original 1 to 10 direct bond oxy-chain chain or carbon atom state is the direct ideal of the atomic number 丨 ~ 8 is inverse - M - extension of each other 'more than two non-contiguous two or more methylene substitutions, methyl = benzene = containing the shot ― ― CH = 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝a group represented by a group of 1,2,3,4-tetrahydronaphthalene-2,6-di= and a gendrobium-2,6-diyl group (each group also contains a respective hydrogen atom by a cyano group, a mouse atom, and three The fluoromethyl, trifluoromethoxy or chlorine atom is in the form of trans-M-cyclohexylene, M-phenylene, 3-H,4)-f 3,5-difluoro^1,4- Phenyl, more ideally, is anti-μ-extended cyclohexyl or 1,4~phenyl, especially ideally anti-丨, 4--extension ring. I",Ρβ, L35 ' L36, L37 and 0 are independent of each other. The ideal grievances are single bond, -OCO-, -COO-, -CH2CH2-, -(c, -och2-, -CIi20---ocf2---cf2o- Or -C<-,4 is more ideally a single bond or -CH2CH2-. X'1, Xjz, X", X34, χ35, χ36 and X37 are independent of each other, indicating a hydrogen atom or a fluorine atom 'γ31, Υ32 and Γ33 is independent of each other and ideally represents a hydrogen atom, a fluorine atom, a gas atom, a cyano group, a thiocyanate group, and the like Single bond, a ch2ch2---(CH2)4- or an OC-, special 23 201217501 trifluoro-foxy, trifluoro-T-based, 2,2,2-three-number 1~12, more ideal The appearance of soil, oxy or carbon atom cyano group, trifluoromethoxy group, tri-n-based group, 2, 2, t, =f, fluorine atom, chlorine atom, the appearance of the base, the ideal sample H is the table Boudoir - rat ethyl or heterozygous number 1 ~! 2 means. : 1 or 2, but q + r and trait ^|^^, ^ and (independent, point of view, jCH = structure in the C three C according to chemical stability - less ideal. Again, look at c C ~ C=C~~ and -CH=CH~ are also less desirable. Moreover, the structure in which the oxygen atom is replaced by a fluorine atom, and the sulfur atom is bonded to the oxygen atom: the sulfur shoulders bond to each other. The structure in which the bonds are bonded to each other is also unsatisfactory. In addition, the structure of the nitrogen-sulfur atom bonding is also less structured, and the nitrogen atom and structure. Specifically, '#卿之_细下频υ Knot

• Υ34 (llla-1) or larva Lr, a subunit of 1 to 8, a carbon atom with a carbon number of 1 to 8, CF2〇H=(cCH2)^38, —〇ch2-, —ch2〇- , - (10) plant, - π indicates that Λ 4 - phenyl phenyl If -1: 4 - cyclohexylene, gas atom, trifluoromethyl, fluoromethyl ^ not 0 or γ 不 乱 齓 齓, 齓 atom, #且的甲气基,二败methoxy or trifluoromethoxy. ) -4d) indicates that the pattern of 1 knot is the following formula (111 b 2a) ~ formula _ 24 201217501

X31

X31 r34—CF20_~<^^—γ34 (l"a-2d) ^X32

(llla-3a) (llla-3c) (llla-3e) X31

(llla-3b) (llla-3d) X31 ^X32

r34hO^O X31 °ρ2^(〇-γ34 ^x32 R34

X32 (llla-3g)

25 201217501

Γ34 (llla-4a) •Υ34 (Hla-4b) γ34 (Hla-4c) Υ34 (Hla-4d) χ32 (wherein: R34 represents the furnace base or the number of carbon atoms 2~8, 1~8, filament, carbon The oxygenated f' subunit of the atomic number ι~8, γ31 face cyano group, each independently, represents a hydrogen atom fluoromethoxy group or a trifluoromethoxy oxo group, a chlorine atom, a difluoromethyl group, a fluoromethoxy group, and a The balance expressed is also ideal.

(R in the gas represents a group having 1 to 8 carbon atoms, gold = original, 〜 yl, γ3, hexacyano, 35Cf 贶methyl, fluoromethoxy, difluoromethoxy or trifluoroantimony. Base.): ', - is a specific structure, and the preferred form of the formula (Illb) is a structure represented by a card type. Under the 26 201217501

27 201217501

F

28 201217501

(wherein R35 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyl group having 2 to S carbon atoms, and Y35 represents a cyano group, a fluorine atom, a chlorine atom or a trifluoro group; Methyl, fluoromethoxy, difluoromethoxy or trifluoromethoxy.) As a specific structure, the preferred embodiment (IIIc) is a structure represented by the following formula.

29 201217501

# , R represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms; an original, a dilute base of \2 to 8, and Y36 represents a cyano group, a fluorine atom, a gas atom, and a trigastone. M-based, difluoromethoxy or trifluoromethoxy. a compound containing at least one selected from the group consisting of compounds represented by the general formula (Ilia), the general formula (Illb), and the general formula (IIIc), and preferably contains a quinone species ~1 〇 species 'Specially ideal is a sample containing two to eight kinds, and the lower limit of the content of the group consisting of the compounds represented by the general formula (Ilia), the general formula (nib) and the general formula (IIIc) is preferable. The state is 5% by mass, more preferably 10% by mass, and more preferably 2% by mass, and the upper limit is ideally 80% by mass, and more preferably 7% by mass. A more desirable form is 60% by mass, and a particularly desirable form is 5% by mass. 30 201217501 Furthermore, in the general formula (IVa), the general formula (IVb) and the general formula (ivc) 矣+ & • 'r41, r42, r43, r44, r45 and r46 are independent of each other, preferably a linear group of 1 to 10 carbon atoms or a carbon atom having 2 to 1 ring, a carbon number of ^ = or an alkenyl group having 2 to 1 S carbon atoms (including the presence of such a group) The fluorenylene group or two or more methylene groups which are not adjacent to each other are substituted or substituted, or one or two or more hydrogen atoms of the fluorene group are substituted with a fluorine atom or a gas atom. Straight bond-like filament, carbon atom ^: 1 〇 straight-chain oxy group or Gu sub-number 2 ~ 丨 (tetra) alkenyl phase is a linear atomic group of carbon number 8 or carbon source ^ = two M44, M45, M46, M47, M, "heart ί ίί anti-M-extension of cyclohexyl (including one methylene group present in the group or two or more sub-mercapto groups which are not adjacent to one another - or -s - H group (including i-CH================================================================= 222] ς辛ς, piperidinar 2,5-diyl, naphthalene-2,6-diyl, hydrazine-tetrahydronaphthalene-μ a group represented by a dinitrogenf-2,6-f group (including a respective group of a hydrogen atom contained in each group, a mouse atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom substituted). , for the reverse: 1,4 - stretching cyclohexyl, M - stretching phenyl, 3-fluoro-M - |, = or 2, 3 - one 齓 1,4 ~ stretching phenyl, more ideally the opposite is ——Extension ring ^ Stretching benzene 4f' 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 理想 。 。

For single bond, CH, L, a, ^ and π are independent of each other, the ideal form is early bond, -CH2CH2---(CH2)4 - OCO---COO___〇CH II, -ch2o 〇cf2 ---CF20- or -oc-, more like the phase 2 -46^' -〇ch2-^ch2o- x;f. w . The eyes are independent of each other, indicating a hydrogen atom or a fluorine atom, (3 means sub-T base Or a 0-, u, v, w, x, y & z are independent of each other, indicating 〇, i or 2, but u + v, w + x and y + z represent 2 or less. (4) formed by the combination of debits In the structure, according to the point f of chemical stability, -CH=CH-CH=CH-, - test - (5) - and -CH=CH-C=c- are less desirable. Furthermore, hydrogen of the structural towels It is also less desirable for the atom to be substituted with a fluorine atom. 31 201217501 is also less desirable, and the structure in which oxygen is bonded to each other, the structure in which sulfur atoms are bonded to each other, and the structure in which a sulfur atom is bonded to an oxygen atom are also less desirable. The structure in which the nitrogen employees are bonded to each other, the structure in which the nitrogen atom is bonded to the oxygen atom, and the structure in which the nitrogen atom and the atomic bond are bonded are also less desirable. 〃 In the compound represented by the formula (pool), Specifically, the ideal form is to kill the following General formula (IVa-1) structure shown.

(wherein R47 and R48 are independent of each other, and represent a group having a carbon number of 丨8, an alkoxy group having a carbon number of 1 to 8 or an alkenyl group having 2 to 8 carbon atoms, L5G, L·51 and L. · 52 each independently, indicating a single bond, a CH2CH2---(CH2)4---OGH2---CH20 〆, an OCF2---CF20- or an OC-, M50 means 1,4 - phenyl or ^,1,4—Extension of cyclohexyl, 屮 and Vi are each independent, indicating 〇 or 1 0) More specifically, the preferred form is the following general formula (IVa-2 a) to (IVa ^3i) ) the structure of the representation.

32

In the formula of 201217501 ® j, ' R AR48 is independent of each other, and represents a burnt group having 1 to 8 carbon atoms, a rock-alkali group having 1 to 8 atomic number or a rare carbon group having 2 to 8 carbon atoms. ), the r47 scoop 弇 S S group is more preferably in the form of a carbon number of 1 to 8 fluorenyl or a carbon number of 1 to "spoon in the compound represented by the formula (IVb), specifically, the following represents The structure shown by the general formula (ivb-1). The core of the sample is R49_M51_(|_53.M52)wi_L

(L55_M53)x1_R50 (IVb·1) (wherein R49 and R50 are independent of each other, and represent a group having a carbon number of Η, an alkoxy group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, L52; [η and l54 are independent of each other, indicating a single bond, -CH2CH2---(CH2)4---OCH2---CH20 I, _OCF2----CF2〇- or ~〇C-, Μ51, M52 and M53 Represents 1,4—stretched phenyl or reverse-1,4—extended cyclohexyl, wl &xl is independent, meaning 〇, 1 or 2, but wl +xl is 2 or less.) More specifically, 'ideal The form is a structure represented by the following general formulae (IVb-2a) to (IVb-3f). R49·

F, F

R49 <IVb-2b) (IVb-2d) R49·

(lVb-3a) (IVb-3c) 〇Vb-3e)

R50 (IYb-3d) F (lVb-3〇Rso (IVb-3b) (wherein R and R5Q are independent of each other, indicating that the atomic number is 1 to 8, the charcoal 33 201217501 atomic number 1 to 8 of alkoxy Or an alkenyl group having 2 to 8 carbon atoms.) In the compound represented by the formula (IVc), specifically, it is preferred to have the following formula (IVc-1a) and formula Structure shown by (IVc - 1 b) R51 -|\/|54_^|_56_|\/l55V ^ - L5-~/ N-\ V-<QK(L58-M56)z1-R52 (|Vc .1a)

〆, F R51 -M54_(L56.M55)y1- 〇^K(L58.M56)2rR52 ,

F, F (wherein R51 and R52 are independent of each other, and represent an alkyl group having a carbon number of 8 and an alkoxy group having 1 to 8 carbon atoms or a carbon number of 2 to 8; l56, T57 month τ58夂-CH2CH2- ^ ^(ChI- _〇CH2- -CH2t 0CF2 CF2〇- or one, M54, M55& M56 means 14-phenylene or trans-1,4-cyclohexyl'yl and zi are independent, 〇, 】 or 2, but yl+zl represents 2 or less.) More specifically, the structure of the following general formula (Wc-2a) to (IVc-2g) is known.

R52 (IVc-2b) R52 (IVc-2d) R52 (|VC-2f) is independent of each other, and represents a group of 1 to 8 carbon atoms, an alkoxy group having 1 to 8 atomic number or a number of carbon atoms. , δ alkenyl. / 34 201217501 A compound containing at least one compound selected from the group consisting of compounds represented by the general formula (IIIa), the general formula '(Hlb), and the general formula (He) used as the third component, or selected from the group consisting of The compound in the group consisting of the compounds represented by the general formula (IVa), the general formula (IVb) and the general formula (ivc) preferably contains two kinds of ～1 〇 species, and particularly preferably contains 2 kinds to 8 kinds, the lower limit of the content rate is 5 mass%, and the more ideal state is 10 mass%. The more ideal state is 2〇 mass%, and the upper limit is more reasonable. The state is 8^% by volume, and the more ideal state is 7〇 mass%, and the more ideal state is 60 mass%. The most ideal state is 5〇 mass%. In the liquid crystal composition of the invention of the present invention, the preferred embodiment is (9) 8 to 〇25. In the liquid crystal composition of the present invention, according to the display mode of the liquid crystal display element, there is a positive or negative & The liquid crystal display element in the mva mode is one or less, and more preferably -2 or less. The liquid crystal composition of the present invention has a broad liquid crystal phase difference absolute value), and the liquid crystal phase temperature 厶 = The heart of the heart is 100c or more, and the more ideal form is 12〇〇c or more. The upper limit temperature is _, the shop is more than the machine, and the liquid is on the liquid. In addition, the lower limit temperature of the liquid crystal phase is ideal. The sample is two C, and the pattern is -3{rc or less. u 20C or less 'more ideally, the acne ketals, 'mercaptophosphine oxides and the like, R 4 talents, gallnuts, benzene sulfur酉Classification, Shifen I 〇 类 、, β-naphthylamines, ==哪崎基贝贝 nitro compounds, etc. Stabilizers are used in combination with the same kind of polyaddition polymerization initiators, benzoin _ t二笨甲^ has a starter. 35 201217501 when the amount added 'relative to the liquid crystal group: % range More reasonable, it can be _5~1 mass~0.1% by mass. The ideal form of Berry/draw is 〇.〇3 [Example] ί ^This is the case. Physical properties TN- ▼ » ^ >1 I Μ ΤΓ l»J ΜΆ OW ΙΪΡ /wr> \ ",, on the crystal phase, the composition of the following examples and comparative examples is expressed as follows: < / ° "Tree day w / °". Liquid. The nematic phase-isotropic liquid phase transition temperature (.0 as the liquid dielectric constant anisotropy 丨 refractive index anisotropy frequency 1 kHz rectangular wave transmittance change 10% of the application limit temperature Δε Δη Vth Voltage (threshold voltage) (Synthesis Example 1) Adding a person to a reaction vessel equipped with a Na apparatus, a cooling crucible, and a thermometer; Fluorine Hope 19.1 g (l〇〇 mmol), 曱 曱 曱 〇 〇 2 ^ Λ ^^ ice, keep the reaction vessel below 5 ° C. Under nitrogen atmosphere: slowly drip ', :,, two or two wind - Ban - Pai Nan 1 〇 g. After the end of the drop, make the reaction vessel The reaction mixture was washed with pure water and saturated saline solution, and the organic layer was dried with sodium sulphate as a solution of sulfuric acid to reduce the amount of the compound represented by the formula (1).

(1) A compound shown in the above formula is added to a reaction vessel equipped with a stirring device, a cooler and a thermometer, and 13.7 g (50 halo), p-hydroxybenzene benzoic acid 8% (6 〇 millimolar), potassium carbonate are added. 10 g (75 mmol), 笨triphenylphosphine palladium lg, tetrahydrofuran 2 〇〇 ml', pure water 100 ml 'The reactor was heated to % under a nitrogen atmosphere. The reaction is carried out. After the completion of the reaction, ethyl acetate was added, and the organic layer was washed with a 5% aqueous hydrochloric acid solution, purified water and saturated brine. After removing the solvent, it was purified by using a two-fold (by weight) alumina column to obtain 7 g of the compound represented by the formula (2). , 36 (2) 201217501

Further, 7 g (24 mmol) of the compound represented by the above formula (2), 2.3 g (26 mmol) of methacrylic acid, and a mercaptoamine group were added to a reaction vessel equipped with a stirring device, a cooler and a thermometer. 300 mg of diazepam and 100 ml of dioxane were placed, and the reaction vessel was kept at 5 ° C % in an ice bath. Under a nitrogen atmosphere, diisopropylcarbodiamine 3.7 g (26 m mole) was slowly added dropwise. After the completion of the dropping force σ, the reaction vessel was returned to room temperature, and the reaction was carried out for 5 hours. After the reaction mixture was filtered, hexane (8) (5) was added to the filtrate, and the mixture was washed with a 5% aqueous solution of hydrochloric acid, and further washed with brine, and dried over anhydrous sodium sulfate. After the solvent was distilled off, it was purified by a two-fold (by weight) alumina column. By recrystallization from dichloromethane/hexane, 6.8 g of the compound of the formula (3) was obtained.

Then, 6.8 g of the compound represented by the above formula (3) and 100 ml of tetrahydrofuran were placed in a reaction vessel equipped with a stirring device, a cooler and a thermometer, and 100 ml of a methanol solution of guanidine hydrochloride was slowly added dropwise. After the completion of the dropwise addition, the reaction was carried out for 1 hour. After completion of the reaction, ethyl acetate and THF were added, and the mixture was purged with 10% aqueous hydrochloric acid, pure water and saturated brine.

Wash the organic layer. After distilling off the solvent, it was purified by using a two-fold (by weight) hydrazine gel column to obtain 4.7 g of the compound (4). Next, '4.7 kg (17 mmol) of the compound represented by the above formula (4), 1.8 g of chloroacrylic acid (20 mmol =), and 50 ml of dichloromethane were placed in a reaction vessel equipped with a stirring device, a cooler and a thermometer. The reactor was cooled to below 5 ° C under a nitrogen atmosphere. Next, 2 g of triethylamine (20 mmol) was slowly added dropwise. After the completion of the dropwise addition, the mixture was reacted for 2 hours at 2 (TC). After the completion of the reaction, dichloromethane was added, and the organic layer was washed with a 10% aqueous hydrochloric acid solution, purified water and saturated brine. Weight ratio) 37 201217501

The ruthenium gel column was purified, and 5.1 g of the target compound represented by the formula (3) was obtained by recrystallization from dichloromethane. The melting point of the compound is: (10). c. (physical value) H-NMR (solvent: deuterated gas): δ: 2 〇5 (s, Qiu, 5 78 (S, 1H), 6.06 (d, lH), 6.36-6.38 (m, 2H), 6.65 (m, lH), 7.19-7.24 (m, 3H), 7.33 - 7.39 (m, 2H), 7.55 (d, 2H) 13C-NMR (solvent: deuterated gas): δ: 18·3, 115.2, 115.4 , 122.0, 122·9, 123.4, 126.9, 127.4, 128.0, 133.5, 136.9, 137.1, 139.9, 150.8, 152.9, 155.3, 163.5, 165.6 Infrared Absorption Spectrum (IR) (KBr): 2925, 1760, 1652—1622, 809 cm-1 melting point: 108 ° C (synthesis example 2)

Formula (6) was obtained in the same manner as in Example 1 except that 14.5 g (100 mmol) of 4-bromophenol was used instead of the 4-bromo-2-fluorophenol 19.1 g (100 mmol) of the Example. The target compound shown is 4.2 g. The compound has a melting point of 132. (: (physical value) H-NMR (solvent: deuterated chloroform) j: 2.08 (s, 6H), 5.77 (silH), 6.04 (d, lH), 6.36-6.38 (m, 2H), 6.66 (m) , lH), 7.17-7.23 (m, 4H), 7.55 (d, 4H) 13C-NMR (solvent: deuterated gas imitation): δ: 18·3, 121·9, 127.3, 128.1, 135.8, 138.0, 150.3, 152.3 ,163.5,165.6 '

I Infrared Absorption Spectrum (IR) (KBr): 2925, 1760, 1652-1622, 809 (^-1 Melting point: 132 ° C (Synthesis Example 3) Adding 2 to a reaction vessel equipped with a stirring device, a cooler and a thermometer Ethyloxy-6-naphthoic acid 23g (100 millimolar), p-hydroxyphenyl methacrylate 38 below 201217501 Temple. Under a nitrogen atmosphere, slowly add diisopropyl carbon dioxide to the end. After that, the reaction vessel was returned to room temperature, and the reaction was carried out for 5 hours. After filtering the reaction solution, U 5 〇 / 〇 «, W was added to the filtrate, and the solvent was used to remove the solvent. Ratio of alumina column iiitg fine _ dichloromethane / has been recrystallized and won the battle (7)

(7) In the reaction vessel equipped with the mixing device, the cooler and the thermometer, the compound of the above formula (7) = 29g (74 millimoles), the second gas group 1GGml, and the environment is tempered with dibutylamine 5.9g. (81 millimoles). After the completion of the dropwise addition, the reaction vessel was returned to room temperature, and the reaction was carried out for 2 hours. After completion of the reaction, the organic layer was washed with a 10% aqueous hydrochloric acid solution, purified water and brine. After distilling off the solvent, it was purified by using a double-stranded (by weight) ruthenium gel column, and 23 g of the compound represented by the formula (8) was obtained by recrystallization from di-methane/hexane. t H°~^i〇_KH3 (8), and then, in a reaction vessel equipped with a stirring device, a cooler, and a thermometer, 23 g (66 mmol) of the compound represented by the above formula (8), and 7.lg of chloroacrylic acid were added. (79 mmol) J dioxane 250 ml, the reactor was cooled to below 5 ° C under a nitrogen atmosphere. Then, 8 g of triethylamine (79 mmol) was slowly added dropwise. After the completion of the dropwise addition, the reaction was carried out for 3 hours at 2 ° C or less. After completion of the reaction, dichlorohydrazine was added, and the organic layer was washed with water containing ι〇% hydrochloric acid, pure water, and saturated brine. After the solvent was distilled off, it was purified by a two-fold amount (weight ratio) of a celite gel column, and 26 g of the target compound represented by the formula (9) was obtained by recrystallization from dichlorohydrazine/decyl alcohol. This compound exhibited 137. (: a broad nematic phase to 193 ° C. 39 201217501 . (physical value) H-NMR (solvent: deuterated chloroform): 5: 2.05 (s, 3H), 5.77 (s,: lH), 6.07 ( d,lH), 6.37 - 6.43(m,2H),6.66(d,1 H),7' 19 — 7.22(m,2H),7.25 — 7.32(m,2I-I), 7.49(d,lH) , 7.71 (s, lH), 7.90 (d, lH), 8.02 (cUH), 8.21 (d, lH), 8.78 (s5lH) 13C-NMR (solvent: deuterated gas): s: 18.3, 118.6, 122 · 2,122.5,126·1, 126.5.127.4.128.1.130.4.131.0. 131.7.133.1.135.7.136.4.148.2.148.4.1 50.4.164.3.165.0. 165.7 Infrared Absorption Spectrum (IR) (KBr): 2925,1760 , 1652—l: 622, 809 cm-1 Melting point: 137 ° C (Synthesis Example 4) In a reaction vessel equipped with a stirring device, a cooler and a thermometer, 19.0 g (100 mmol) of 4-bromo-catechol was added. 2 g of acridinium sulfonium sulfonate and 50 m of di-methane methane were kept in an ice bath at a temperature below 5 〇c. Under a nitrogen atmosphere, 3,4 - 1 - 2H - brim 20 g was slowly added dropwise. After the completion of the addition, the reaction vessel was returned to room temperature. The reaction was carried out for 2 hours. The reaction solution was washed with pure water and saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 31 g of a compound represented by the formula (10) which protected the hydroxy group.

17.8 g (50 mmol) of the compound represented by the above formula (10), p-hydroxyphenyl boron_: 8.3 g (60 Torr), potassium carbonate 10 g were added to a reaction vessel equipped with a stirring device, a cooler and a thermometer. (75 mmol), triphenylphosphine palladium ig, tetrasylfuran 2 〇〇 ml, 100 ml of pure water, and the reaction was carried out by heating the reactor to 8 yc under a nitrogen atmosphere. After completion of the reaction, ethyl acetate was added, and the organic layer was washed with a 5% aqueous hydrochloric acid solution, purified water, and brine. After distilling off the solvent, it was purified by a two-fold (by weight) alumina column & to obtain 13.8 g of the compound represented by (11). ) 201217501

°H (11), and 'in the reaction vessel equipped with a stirring device, a cooler and a thermometer, add 9g (24 millimolar) of compound represented by formula (2), and maleimide acetic acid 4 to 26 milligrams. Ϊ́ϊ), dimethylaminopyridine 300 mg, dioxane 100 ύ, and the reaction was maintained at 5 in an ice bath. 〇The following. Under a nitrogen atmosphere, diisopropylcarbodiimide &amine 3.7 g (26 mmol) was slowly added dropwise. After the completion of the dropwise addition, the reaction vessel was returned to room temperature for 5 hours. After filtering the reaction mixture, 1 ml of dichloromethane was added to the filtrate, and the mixture was washed with a 5% salt aqueous solution, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, it was purified by using a two-fold (by weight) alumina column. 9.5 g of the compound represented by the formula (12) was obtained by recrystallization from dichloromethane (hexane).

Then, 9.5 g of the compound represented by the above formula (12) and tetrahydrofuran l〇〇ml were added to a reaction vessel equipped with a stirring device, a cooler and a thermometer, and 0.2 ml of a sterol solution i〇ml of hydrochloric acid was slowly added dropwise. . After the completion of the dropwise addition, the reaction was carried out for 1 hour. After the completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with a 10% aqueous hydrochloric acid solution, purified water, and brine. After distilling off the solvent, it was purified by a two-fold (by weight) hydrazine gel column to obtain 5.2 g of the compound (13). Next, '5.2g (15 millimolar) of the compound represented by the above formula (13), 2 g of chloroacrylic acid (2 〇 millimolar), and 2 m of methane 50 m were added to a reaction vessel equipped with a stirring device, a cooler and a thermometer. The reactor was cooled to 5 under a nitrogen atmosphere. 〇The following. Then, slowly add 3 g of triethylamine (20 house moles). After the completion of the dropwise addition, the reaction was carried out for 3 hours under 2 °C. After completion of the reaction, dichlorosilane was added, and the organic layer was washed with a 1% aqueous hydrochloric acid solution, 41 201217501 pure water: saturated brine. After purging the solvent, it was purified by using a double-strength (weight ratio) Shishijing knee column, and recrystallized from methylene chloride/methanol to obtain 3 g of the target compound represented by the formula (14).

(Synthesis Example 5) In a reaction vessel equipped with a stirring device, a cooler, and a thermometer, a compound represented by gallic acid, 7 g (100 mmol), triethylamine 36 g (36 Torr mmol), and di-methane were added. 500 =, the reactor was cooled to below 5 〇c under a nitrogen atmosphere. Then, 37.6 g of methyl methacrylate (36 〇 millimolar) was slowly dropped. After the completion of the dropwise addition, the reaction was carried out for 3 hours under the fox. After the completion of the reaction, dichloromethane 2 was added to remove hydrazine. The organic layer was washed with a hydrochloric acid solution, pure water, and a saturated saline solution. After the solvent was aged, it was purified by using a ruthenium gel column of 2 times by weight, and was obtained by dispersing the methane/hexane. (15) The target compound shown is ringing.

Then, in the reaction vessel of the scale device, the cooler and the thermometer, add the compound, (15) the compound 16g (50 millimoles), 4__(4 propylene oxyphenyl)-alumina Acrylic acid 1 twist (5 〇 millimolar), dimethylaminopyridine 3 〇〇 mg, dichloromethane l〇〇m 丨, the reaction is held in the ice bath below the sink. Slowly under nitrogen atmosphere = bis(diisopropylcarbodiimide) 7.5 g (10) millimolar). After completion of the dropwise addition, the reaction was allowed to return to room temperature, and the reaction was carried out for 5 hours. After filtering the reaction mixture, 300 ml of a decane was added to the filtrate, and the mixture was washed with a 5% aqueous solution of hydrochloric acid, and further washed with a saturated aqueous solution of water. After distilling off the solvent, it was purified by a two-fold amount (weight j) of oxygen, and 18.2 g of the compound represented by the formula (16) was obtained by recrystallization from the dichlorobenzene/hexane. 42 (16) 201217501 person (synthesis example 6)

For 140 ° C (17) hK ^ ° x (Synthesis Example 7), methacrylic acid and 4,4'-biphenol were reversed in the same manner as in Synthesis Example (1). The title compound. The melting point of the compound is 153. h hK-o^Hh3 (18) (Example 1)

Oc2h5 C5Hu OC2II5 10% OC2H5 15% A liquid crystal composition LC-1 containing a compound selected from the general formulae (IVa-1) and (IVb-1) was prepared. The composition of the compound and the ratio of the content are as follows.

15% 15% 5% 10% CH3 10% 10% 10% The physical properties of the liquid crystal composition LC-1 are shown in Table 4 [Table 4] 43 201217501

Tn-i (C) 72 Δε -3.3 Δη 0.086 The polymerization property was adjusted by adding 0.3% of the polymerizable compound represented by the synthesis example (1) to 99.7% of the liquid crystal composition, and uniformly dissolving the polymerizable compound. The physical properties of the liquid crystal composition CLC-bCLC-1 are almost the same as those of the above-mentioned lC-丨. The CLC-1 was injected into the cell gap of 3 5 μm by a vacuum injection method and coated in a ΙΤ0-type cartridge which caused a vertically oriented polyimide film. After measuring the pretilt angle of the cartridge (crystal rotation method), a rectangular wave of h8v was applied at a frequency of 1 Torr, and the material (4) and the wire of the Γ0 Γ or less were filtered out, and the liquid crystal cell was irradiated to the outside of the liquid crystal: ^. Adjust the box table _ to the strength of the material SQmW / W and illuminate 6 〇. The second deduction is a vertical alignment type crystal display element which polymerizes the polymerizable compound in the polymerizable liquid crystal composition. After that, the component was decomposed, and the amount of residual monomer of the liquid crystal composition was measured by high-efficiency hybrid (muscle C: solvent acetonitrile). The monomer before UV irradiation is 0.3%. The monomer after UV irradiation is 0.02%. The polymerizable compound proceeds sufficiently without the polymerization of the photopolymerization agent. Further, the liquid crystal cell is accompanied by an ultraviolet ray pre-tilt m (four) rotation method) and the electro-optical characteristics of the device are determined as follows. ^ --- - j Pre-tilt angle before irradiation 0 Pre-tilt angle after irradiation 87.0 Vth (V) 2.40 "It is known that a polymerizable compound is polymerized to obtain a vertical alignment liquid crystal display element having a molecular pretilt. And it was passed (Example 2) 201217501 Chemical compound 1 " 7% 'Addition of the polymer CLC 2 ^ hook' shown in the synthesis example (5) to modulate the physical properties of the polymerizable liquid crystal composition in acres*, + There is almost no difference from the physical properties of LC-1 described above. The human method uses the same method as the embodiment 丨 to determine the gap between the two chambers and the coating box. In the liquid crystal composition, the amount of residual monomers was very small, and the amount of residual monomers was very small, and the monomer was 詈0.3% after the irradiation of the wire. Further, the results of the measurement of the electro-optical characteristics of the surface before and after the irradiation of the material lines of 70 and 70 were shown in Table 5. \AJ] Pre-tilt angle before ultraviolet irradiation 89.0 Pre-tilt angle after ultraviolet irradiation 84.0 ^V) ^2.80 It can be seen from the above results that the vertical alignment liquid crystal imparting pre-tilt of liquid crystal molecules is obtained by merging and combining Display component. (Comparative Example 1) The polymerizable liquid crystal composition CLC-3°CLC was prepared by adding 0.3% of the polymerizable compound represented by the synthesis example (6) to the liquid crystal composition LC-199.7% and uniformly dissolving it. The physical properties of -3 are almost the same as those of the above ι^-丨. The CLC-3 was injected into the cassette by a vacuum injection method at a gap of 3.5 μm and coated with a polyimide film which caused the orientation of the polyimide. After the pretilt angle of the cell (crystal rotation method) was measured, a rectangular wave of 1.8 V was applied at a frequency ,, and a filter having ultraviolet rays of 320 nm or less was filtered out, and the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp. The irradiation intensity of the surface of the cell was adjusted to 50 mW/cm2 and irradiated for 6 sec. to obtain a vertical orientation for polymerizing the polymerizable compound in the polymerizable liquid crystal composition. Thereafter, the element was decomposed, and the result of measuring the residual monomer amount of the liquid crystal composition by high performance liquid chromatography (HPLC: dissolution) was shown in 6.

[Table 6J: 0.3% of the monomer before the ultraviolet irradiation, and 0.04% of the monomer after the ultraviolet irradiation. From the above results, it is understood that the polymerization of the polymerizable compound of the synthesis example (6) proceeds without the photopolymerization initiator. There is a large amount of monomer remaining. Further, the pretilt angle (crystal rotation method) before and after the ultraviolet irradiation of the liquid crystal element and the measurement results of the elements are shown in Table 7. Pretilt angle before ultraviolet irradiation ^9.3 ^Pretilt angle after line irradiation 87.2 Vth(V) ' 2.42 Give liquid crystal molecules a pretilt _ money to the residual crystal _ component. Dissolved Ϊί: The liquid crystal composition was stored at - 2 〇〇C for three days to precipitate crystals, and it is known that [Simplified description of the drawing] None [Main component symbol description] 46

Claims (1)

201217501 VII, the scope of application for patents: 1. A liquid crystal display element, you can use a pair of substrates to control the use of two, there is control by the gap of the liquid crystal cell can be applied, the liquid crystal layer contains liquid crystal driven by voltage The structure of the layer; the polymerizable compound composed of the liquid crystal molecules composed of the liquid crystal molecules of the object (A) and the two types of energy, is a combination of one or two kinds of the tilt of the scorpion in the polymerizable compound. The hardened compound; (8) in the molecule _ 2 _ = = (= the poly = 3 or more traces are 2 or the voltage applied between the substrates while the 'inside-side control between the substrates ! Kind or: in the state of 'the polymerized silk (9), the crystallized branch 1 thief 2 or more of the 3 factories, such as the long-term accounting of the liquid of the patent range 丨 or 2 relative to the substrate flat 2 normal 4 The application of the patent scope 1 or 2, a _ _ n, so that the short-axis direction of the liquid crystal molecules is normal with respect to the plane of the substrate &< 2 5. As in any one of the claims 1 g of liquid crystal molecules in the liquid layer f Γΐ ,, the hardened matter is (10) ~ 〇 two g, 6. The liquid crystal display element according to any one of the first to sixth aspects of the present invention is polymerized by ultraviolet light having a wavelength of 280 to 400 nm. ', and 4_8. ^1 The liquid crystal display element of the 1st to 7th items of the towel is polymerized at a dose of 4000mJ/cm or less. In the middle of the product, please refer to any of the first to eighth patents. In the liquid crystal display device, the polymerizable functional group of the 'sex compound (Β) is one of the formula (R-1}~form d, B) 47 201217501; 1〇, (R-1) ημ .0. Ο (R-2) V (R-3) or 〇 CT (R-4) (R-5) HSC cr 0 (R-6) (4) H3c 0 ch3 (R-8) Ό· Η〗. , r, <y H3CV (R-9) (R-l〇) • I 0 /N~w HS— O (R-14) (R-11) (R-12) (Rl 3) In the liquid crystal display element 4 of the items 1 to 8 of the application range, the colloidal material (9) A polymerizable functional group having the formula (R-1) and (R-2). 'inch ~ consumption solid 9th 11 · as claimed in the patent scope of item W0 - liquid crystal display 1 = polymerizable compound (9) has at least one species represented by the general formula (Α - 丨) ~ (α - 4) , X" X12, (R-15) X'4 X13 (A-l), 11 X12 X15 X16 (A-3) C13 X14 X^X18 (»12 v]3 (A-2) (A-4), the silk (tetra) group of the carbon atom number 丨8 of the atomic group of the Nanxie branch, the burning atom, the -c=c---oc--- C〇〇: T-hetero-arylene group can break the hydrogen atom in the alkyl group and can be substituted by the ii-based group. C0—4 s—substitution, 12. In the middle of the first to eleventh patent application, the polymerizable compound (B) is a liquid crystal display element represented by the formula 1 and is converted to j, 201217501 (ρ^αι_βι_ (_α2—B2七_a3h (I) m (wherein P and P2 are each independently and represent any of the polymerizable functional groups represented by R_; ) Formula (R-15) Table ^r0, 0 (Rl) CH, 0, 0 (R-2) CF, 0, 0 (R-3) (R-4) cr h3c h3c (R-5) Cr (R-10) (R-9) (R-6) (R-in (R-7) ch3 (R-8) ^ (R_12) (R-13) (R-14) (R., 5) t When there are multiple pi and / or P2, these can be the same Both pl and p2 of the Hi moiety represent the same polymerizable functional group; mono-i 3 4 is independent, and represents M-phenyl, benzene-I#-triyl, benzo-U, 4, f-tetra, M —Extension of cyclohexyl, cyclohexan-1,3,5 —- t-member-1,3,4-diyl, cyclohexane-L3,4,5-tetrayl, ° pyridine-2,5 — j = Ή, 5_二基, 蔡-2,6-diyl, Cai-2,5,6-triyl, naphthalene',-tetrayl, I,2,3,4-tetrahydronaphthalene-2 6 —Diyl, 1,2,3,4-tetrahydronaphthalene- 2 5 1 group, 1, 2, 3, 4 — 4 虱 Qin 2, 5, 6, 7 — 4 or ΐ, 3 — 2 Oxygen hydrazine - diyl ' Α 1 and Α 3 are independent of each other and may be unsubstituted or substituted by a halogen atom having 1 to 12 alkyl groups, a halogen atom having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. 1 to 12 of a haloalkoxy group, a halogen, a cyano group or a nitro group; Α represents a phenyl group, a phenyl group, a 1,4-cyclohexylene group, an α ratio β, a 2,5-diyl group, a succinct —yl, naphthalene-2,6-diyl, indane-2,5-diyl, 1,2,3,4-tetra-di-diyl or 1,3-dioxo-indole-2,5-diyl , the base can not be taken from the factory or the private atom number 1~12 'j: complete base a halogenated alkyl group having an atomic number of 1 to 12, 49 201217501 an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, a γ element, a cyano group or a nitro group; For A2, these may be the same or different; B1 and B2 are each independently 'representing a single bond, ——s_, — 〇ch:2—, —ch2o---CO c2h4---coo---oco-, - ocooch2 —, —CH2OCOO—, —CO—NR]1—,―概11—cq—,—sCH2 ~ '—CH2S— '—CH=CRn —COO— x —COO —CRn = CH— ' -CH= CR -OCO-, -OCO - CRU = CH -, -COOC2H4-, -OCOC2H4-, -C2H4OCO-, -C2H4C00-,"-〇c〇CH2-, -CH2COO---CH=CH-, -CF = CH—, —CH=CF—, — cf2 cf2o—-〇cf2---cf2ch2---ch2cf2---cf2cf2—or an OC—(wherein R11 represents a hydrogen atom or a carbon number of 丨~4 When a plurality of B2 groups are present in the alkyl group, the groups may be the same or different; the fields m1 and m2 are each independently, indicating 1, 2 or 3; η represents 〇, 1 or 2). 13. A liquid crystal display element according to any one of the items 1-4 to 12 of the patent application, wherein a compound represented by the formula (Π) is contained in the pot as a liquid crystal group R2'-Μ21-L2Μ22- (L22 - Μ23),, - R22 (Π) Mountain (wherein, R21 and R22 are independent of each other, and the number of carbon atoms, U1〇, the number of the anodic atoms of 2S10, which is the number of carbon atoms, is present in the bases. The alkylidene group having a methyl group of (10) or more may be substituted with - or -s-, or a group of two or more hydrogen atoms may be substituted with a fluorine atom or a gas atom; and the groups M and M1 are independently of each other, and are selected from 2 (a) trans-1,4-cyclohexylene in the group of the following composition (the methylene or more indenyl groups present in the group may be substituted by _〇- or -s-), : Next, w(b)1,4—stretching phenyl (one -CH= or two or more non-contiguous -CH=substitutable nitrogen atoms present in the group), 2-fluoro-1,4- Stretching base, 3 翁 个 ^ — stretching base, 3,5_difluoro-1,4 —phenylene, and 5 (c)l,4 —cyclohexene, ι, 4 —bicyclo[ 2 2 2] 仲辛基,派啶——一50 201217501 基,奈~2,61-2 base, Hydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2, anthracene-diyl; 〇 represents 0, 1 or 2; L and 1^2 are independent of each other' represents a single bond, CH2CH2-, -(CH2)4-, -〇CH2-, -CH2〇-, -0CF2-, -CF20-, -CH=CH-, -CIi=N- or one C^C-, when there are multiple In the case of G2, the same may be the same or different; when there are a plurality of Μ23, the same may be the same or different). The numerical value of the dielectric anisotropy of the liquid crystal display element (A) of the liquid crystal display element (A) of any one of the first to third and fifth to third aspects of the patent application is 2 or more.液晶M1 Patent Application No. 4 of the liquid crystal display element, wherein the liquid crystal composition f is selected from the group consisting of compounds represented by the general formula (IIIa), the general formula (IIIb) and the general formula (service) Compound; r31 R31-M31-(L31.M32)p.L32_^_Y31 (nia) X32 X35 A ϋϋ, /32 and r33 are independent of each other, and the corpses of the number of carbon atoms 1 to i 在 are in the two #„代_子 or = are selected from the following: medium: base: Μ", Μ37 and Μ are independent of each other, and more than one of the above-mentioned fluorene groups are stored in m methylene groups or not adjacent to one of the existing ones on 201217501—CH= or two non-contiguous ones with = base: ί is,), 3-gas-'extension (four)^, the tetrahydronaphthalene-2,6-diyl and decahydronaphthalene-2,6- 3 (e) or the hydrogen atom in the group (f) can be cyanide Substituted by a fluorine atom, a difluoromethyl group, a trifluoromethoxy group or a gas atom; Γγίη, L, a, L34, a, L36, I" and π are independent of each other, and represent a single bond, -〇CO-, CH2CH2—(CH2)4—, _〇cH2—, — 372 3: —, —CF2〇—or —CSC~, when Μ32, Μ34, Μ35, or the same may be different; when there are multiple L and/or L These can be phase #X, X32, χ33, χ34, χ35, χ36 and χ37 are independent of each other, indicating a nitrogen atom or a fluorine atom; ir32 -ry "ΙΟ: Υ and γ are independent of each other, and represent fluorine atom and gas Atom, cyano, thiocyano, trifluoromethoxy, trifluoromethyl 2,2,2-trifluoroethyl or difluoromethoxy; P, q, r, s and t each independently, represent square, 1 or 2, and q + r and s + t is 2 or less). 16. The value of the dielectric anisotropy of the liquid crystal display element 'in the liquid crystal composition (A) according to any one of the claims 1, 2, 4 to 13 is one or less. 17. The liquid crystal display device of claim 16, wherein the liquid crystal composition (8) is selected from the group consisting of compounds represented by the general formula (IVa), the general formula (IVb), and the general formula (IVc). a compound in the group; 201217501 χ42 v41 R41_M41_(L41.M42)u_L42. (L43_M43)v_R44 (IVa) R42-M44-(L4(M45)W- L45 (L46.M46)x_R45 (IVb) R43-M47 one (|_47_M48)y_ L48 (L49_M49)z-R46 (IVc) (wherein R41, R42, R43, R44, R45 and R46 are independent of each other, and a pit group having a number of 1 to 10 or an alkenyl group having 2 to 10 carbon atoms; Two or more methylene groups adjacent to ^1 in the same group may be substituted with ~〇2 or :s 1 gas original ΐ. One or more hydrogen atoms may be substituted for riding atoms or representing == two. , Μ47, Μ48, and 立立, one of the two adjacent to each other, two non-adjacent ones, the hexavalent base, the Μ-double ring [2.2·2], the octyl group, the pie. 5-But the nitrogen in the J group, 1,2,3,4-tetrachloroca-2,6-diyl and decahydronaphthalene-2 6-indene, yl, (h) or (1) Each atom may be substituted by a cyano group, a fluorine ', a fluorenyl-fluorenyl group, a trifluoromethoxy group or a gas atom; a single bond, -ϋ ' L 4, L45, L46, L47, and L49 are independent of each other, -CH Ο '〇C〇·" ' ~CH2CH2~ ' -(CH2)4~ ^ -〇CH2 -- 2 , —〇CF2', —CF20—or —〇C—, when Μ42′ Λ/γ43 53 201217501 X41, X42, X43, X44, X45, X46, X47 and X48 are independent of each other and represent a hydrogen atom, a trifluoromethyl group, a trifluoromethoxy group or a fluorine atom. Any one of X41 and X42 represents a fluorine atom, and any of X43, X44 and X45 represents a fluorine atom, and any of X46, X47 and X48 represents a fluorine atom, but X46 and X47 do not simultaneously represent a fluorine atom, X46 And X48 does not represent a fluorine atom at the same time; G represents no fluorenyl or a 0-; u, v, w, X, y, and z are independent of each other, indicating 0, 1, or 2., but u + v, wj + x and y + z are 2 or less). 54