TWI375093B - Optical compensation sheet, process for producing it, polarizing plate - Google Patents

Description

1375093 IX. Description of the invention: [Technical division of the invention] The present invention relates to an optical 'compensation sheet, a polarizing plate and a liquid crystal display device, and more particularly relates to a liquid crystal display device, particularly a vertical alignment (VA) mode liquid crystal display. An optical compensation sheet and a polarizing plate having a viewing angle characteristic of the device, and a liquid crystal display device having improved viewing angle characteristics. Further, the present invention also relates to a method of manufacturing an optical compensation sheet having good optical compensation ability. [Prior Art] As a display device used in an OA device such as a word processor, a notebook personal computer, or a monitor for a personal computer, a portable terminal device, a television, or the like, a CRT (Cathode Ray Tube) is mainly used. In recent years, liquid crystal display devices have been widely used in place of CRTs because they are thin, lightweight, and consume a small amount of power. The liquid crystal display device has a liquid crystal cell and a polarizing plate. The polarizing plate is composed of a protective film and a polarizing film, and a polarizing film made of a polyvinyl alcohol film is dyed with iodine and stretched, and a protective film is laminated on both surfaces thereof. For example, in a transmissive liquid crystal display device, the polarizing plate is usually mounted on both sides of a liquid crystal cell, and one or more optical compensation sheets are further disposed. On the other hand, in the reflective liquid crystal display device, a reflecting plate, a liquid crystal cell, one or more optical compensation sheets, and a polarizing plate are disposed in this order. The liquid crystal cell is composed of liquid crystal molecules, two substrates for encapsulating it, and an electrode layer for applying liquid crystal molecules. Since the alignment state of the liquid crystal molecules of the liquid crystal cell is different, the display is ON and OFF. There are proposals that can be applied to any of transmissive, reflective, and semi-transmissive types such as TN (Twisted Nematic), IPS (IPS (Intraplane Switching), OCB (Optically Compensated Birefringence), VA (Vertical Discharge) IJ), ECB (Electrically Controlled Birefringence 1575093 is applied in a roll-to-roll manner, which significantly increases the cost. As a solution, for example, there is a so-called cross-section that is stretched in a direction orthogonal to the MD (TD direction). Stretched film, transversely stretched film is prone to the occurrence of a slow-axis axis skew called bowing. Since the yield cannot be increased, the cost increases. Furthermore, since the adhesive layer is used in the laminate of the stretched film, the temperature and humidity are maintained. The change in the adhesive layer causes the adhesive layer to shrink, and the film may be peeled or warped, etc. As a method of improving the method, a method of applying a rod-like liquid crystal to form an a-plate is known (refer to Patent Document 2). In recent years, there has been proposed a combination of a c-plate and an a-plate, and a method of using a biaxial phase difference plate (Non-Patent Document 2). By using a biaxial phase difference plate, not only can the contrast be improved. View angle and also has excellent color tone However, in order to produce a biaxial stretching of a general biaxial retardation plate, it is difficult to control a uniform axis in the entire region of the film as in the case of the lateral stretching, and since the yield cannot be increased, the cost increases. A method of producing a biaxial retardation plate by stretching without using a method of irradiating polarized light by a special cholesteric liquid crystal (Patent Document 3) or a method of irradiating polarized light by a special dished liquid crystal (Patent Document 4) This method can solve various problems caused by stretching. However, the biaxial retardation layer 'produced by the method of irradiating polarized light to the liquid crystal coating material is problematic in terms of the adhesion of the transparent support, which is problematic. The optical compensation sheet which is a laminate of the biaxial retardation layer and the transparent support is a problem to be solved from the viewpoints of manufacturing suitability, stability over time, and the like in the case of bonding to a polarizing plate. In addition, in the case of manufacturing a phase difference plate using a liquid crystal coating material, in order to align liquid crystal molecules, a layer of 1375093 alignment layer may be disposed directly under the liquid crystal molecules. However, in general, polyethylene is used. In the case of an alcohol or a polyimide-like alignment layer, the adhesion between the alignment layer and the layer formed of the liquid crystal coating material is insufficient, and similarly to the above, the suitability for bonding to a polarizing plate or the like* or From the viewpoint of stability over time, etc., there are many problems. Further, when a layer composed of the liquid crystal coating material is irradiated with polarized light to be manufactured in a biaxial retardation plate for optical compensation, the surface of the film is used. There is a problem in the shape, that is, there is a problem of unevenness, and various kinds of misalignment occur. V [Patent Document 1] Japanese Patent Laid-Open No. Hei 2-7 7662 No. 5 [Patent Document 2] JP-A-2000-3 0493 No. 0 [ [Patent Document 3] International Publication No. WO 003/054111 [Patent Document 4] JP-A-2002-6138 [Non-Patent Document 1] SID 97 DIGEST 845 pages to 848 pages [Non-Patent Document 2] SID 2003 DIGEST 1208 pages ~1 Pp. 211 [Invention] The problem of the first aspect of the present invention is to provide optical compensation for liquid crystal cells accurately and to be used even if the number of sheets is small. Optical compensation sheet in thin layer liquid crystal display element, suitable for manufacturing Bis excellent and its improved stability and biaxial optical compensation sheet, and the method of stably producing the optical compensation sheet. Further, a polarizing plate and a liquid crystal display element using the optical compensation sheet, in particular, a VA mode liquid crystal display element are provided. An object of the second aspect of the present invention is to provide an optical compensation sheet which can be optically compensated for a liquid crystal cell and which can be used in a thin layered liquid crystal display element even if it is bonded in a small number of sheets. An optical compensation " sheet of 1475093 which has improved biaxiality and uniformity of film and reduced plaque, and a stable manufacturing method of the optical compensation sheet. Further, the present invention provides a polarizing plate and a liquid crystal display element using the optical compensation sheet, in particular, a VA mode liquid crystal display element. Means for Solving the Problem A first aspect of the present invention relates to an optical compensation sheet comprising a transparent support, coating a solution of a solvent of 20% or more of water on the transparent support*, and forming a high by drying. a molecular layer, and an optically anisotropic layer formed thereon by a liquid crystal composition containing at least one liquid crystal compound, wherein the front side retardation (Re) of the optically anisotropic layer is non-zero, relative to The in-plane delay " phase axis is the normal direction of the optical compensation sheet of the tilt axis (rotary axis), and the hysteresis measured by the light incident at a wavelength of ληπι in a direction inclined by +40°, and The in-plane slow phase axis is taken as the normal direction of the optical compensation sheet of the tilt axis (rotation axis), and the 'hysteresis 测定 measured when the light of the wavelength ληπι is incident at an oblique angle of -40° is substantially equal, and the The polymer layer is chemically bonded to the optically anisotropic layer. Further, a second aspect of the present invention relates to an optical compensation sheet comprising a transparent support, a polymer layer on the support, a surface containing at least one liquid crystal compound and at least one fluorine-containing level on the surface of the polymer layer An optically anisotropic layer formed by a liquid crystal composition of an alignment agent, wherein a front retardation Re(Re) of the optically anisotropic layer is non-〇, and is a tilt axis (rotary axis) with respect to an in-plane retardation axis The normal direction of the layer plane is from +40. The hysteresis 测定 measured when the light of the incident wavelength ληπι is incident in the oblique direction is inclined from -40° from the normal direction of the layer plane which is the tilt axis (rotation axis) with respect to the in-plane slow axis. 10- 1375093 The hysteresis 测定 measured when the light of the incident wavelength ληιη is incident is substantially equal. The fluorine-containing horizontal alignment agent may be a discotic compound or a compound represented by any one of the following formulas (I) to (ΠΙ). Formula 4

• R2 where 'R1, R2 and R3 each independently represent a hydrogen atom or a substituent, at least one substituent representing a fluorine atom, and X1, X2 and X3 represent a single bond or a divalent linking group; Formula (11)

Wherein R 2 i , R 22 ' , R 24 and r 25 each independently represent a hydrogen atom or a substituent, and at least one substituent representing a fluorine atom; Formula (ΠΙ) [Formula 6] Formula (111) -11- 1375093 a method for producing an optical compensation sheet according to the above first aspect of forming a chemical bond: a method of sequentially applying a discotic liquid crystal containing at least one polymerizable group on a surface of a polymer layer formed on a transparent support a step of aligning the compound and the liquid crystal composition of the at least one fluorine-containing horizontal alignment agent, aligning the molecules of the discotic liquid crystal compound with an average tilt angle of less than 5°, and irradiating the polarized light to make the discotic liquid crystal compound a method for producing an optical compensation sheet according to the second aspect of the step of polymerizing to form an optically anisotropic layer; and performing the coating on the surface of the polymer layer formed on the transparent support in the order of * The step of containing at least one liquid crystalline composition of a rod-like liquid crystal compound having a polymerizable group and at least one fluorine-containing horizontal alignment agent, the molecule of the rod-like liquid crystal compound being less than 5. The method of manufacturing the optical compensation sheet of the second aspect in which the average tilt angle is a cholesteric alignment step and a step of irradiating the polarized light to polymerize the molecules of the rod-like liquid crystal compound to form an optically isotropic layer. Moreover, from another point of view, according to the present invention, there is provided a polarizing plate having at least one optical compensation sheet and a polarizing element of the first or second aspect; and a liquid crystal display device comprising the first or second The optical compensation sheet of the aspect, the optical compensation sheet of the first or second aspect, and the polarizing element; and the above liquid crystal display device, wherein the display mode is VA mode. [Embodiment] Hereinafter, the present invention will be described in detail. In the present specification, the term "~" is used as the lower limit 値 and the upper limit 包含 including the number described before and after. Further, unless otherwise specified, the % of the content is expressed by mass%. In this specification, Re hysteresis and Rth hysteresis are calculated according to the following 1375093. Re(X) and Rth(X) indicate hysteresis in the in-plane hysteresis of each wavelength λ and hysteresis in the thickness direction. Re(X) is measured by KOBRA 2 1 AD Η (manufactured by Oji Scientific Instruments Co., Ltd.) in which light of a wavelength ληπι is incident on the normal direction of the film. Rth〇) * is based on the above ReU) and the slow axis (determined by KOBRA 21ADH) as the • tilt axis (rotary axis), which is +40 from the normal direction of the film. The direction of the tilt The hysteresis 测定 measured by incident light of the wavelength ληπι and the in-plane slow axis as the tilt axis are -40 from the normal direction of the film. In the direction of the tilt, the hysteresis 测定 measured by the incident light of the wavelength ληπι is measured by the KOBRA 21ADH based on the measurement of the delay _ 値 in three directions. At this time, it is necessary to input the assumption of the average refractive index and the film thickness ^ KOBRA 21ADH system in addition to Rth (X), also calculate the average refractive index of nx, ny, nz 系 using cellulose acetate 丨.48 'but as cellulose acetate The polymer film of representative optical applications other than 値' may be a cyclic olefin polymer (1.5 2), a polycarbonate (1.5 9), a polymethyl propylene methyl ester (1.49), or a polystyrene (1.59). Wait a minute. The average refractive index of other existing polymeric materials can be obtained using the Polymer Handbook (j〇hN WILEY & SONS) or a catalog of polymeric films. Further, in the case of a material having an average refractive index of not clear, it can be measured using an Abbe refractometer. In the present specification, λ 丨 has a special I load ‘ 545±5 nm or 590±5 nm°. In the present specification, the term “substantial” with respect to the angle means that the error with the rigor angle is less than ±10. In the range. Furthermore, the error with the tight angle is preferably less than four. More preferably, the system is less than 3. . The term "substantially equal" as used in the term "hysteresis" means that the difference in hysteresis is within ±1〇%. [Optical Compensation Sheet] Fig. 1 is a schematic cross-sectional view of an optical compensation sheet of the first aspect of the present invention, -15-1375093. The optical compensation sheet of the first aspect of the present invention has an optically anisotropic layer; 12 on the transparent support 11. Between the transparent support 11 and the optically anisotropic layer 12, a polymer layer 13 as an alignment layer function for controlling alignment of liquid crystal molecules in the optically anisotropic layer 12 is disposed. The polymer layer 13 is a polymer layer formed by coating and drying a solution composed of a solvent of 20% or more of water, and is chemically bonded to the optically anisotropic layer 12. Therefore, the adhesion between the polymer layer 13 and the optically anisotropic layer 12 is high, that is, it is difficult to perform peeling or the like in the chemical treatment such as washing or saponification such as water washing, and the handling property is good. . Further, the optical characteristics of the optically anisotropic layer 12 are adjusted such that the front retardation Re(Re) is not zero, and the normal of the optical compensation sheet which is the tilt axis (rotation axis) in the in-plane slow axis is used. The direction of the hysteresis 测定 measured when the light of the wavelength ληπι is incident in a direction inclined by +4〇°, and the normal direction of the optical compensation sheet which is the tilt axis (rotation axis) with respect to the in-plane slow axis. The hysteresis 测定 measured when the light of the wavelength ληηι is incident at an oblique angle of -40° is substantially equal, so that the liquid crystal cell, particularly the liquid crystal cell of the VA mode, can be correctly compensated. Furthermore, Re non-zero means that Re is not less than 3 nm. Fig. 2 is an example of an optical compensation sheet according to a second aspect of the present invention. The optical compensation sheet according to the second aspect of the present invention has a polymer layer 13' on the transparent support 1 1 and an optically isotropic layer 12' on the polymer layer 13'. The polymer layer 13' has a function of an alignment layer for controlling the alignment of the liquid crystal molecules in the optically anisotropic layer 12'. The optically anisotropic layer 12' is formed by coating a composition containing at least one liquid crystal compound and at least one fluorine-containing leveling agent on the surface of the polymer layer 13' so that the molecules of the liquid crystal compound are aligned. -16- 1375093 In combination, the chemical crystals are all right in the following table in the table, and the water surface of the fluorine film is lightly reduced. The composition of the layered composition is also improved in the uniformity of the alignment state of the liquid crystal molecules, so that the optical anisotropy layer 12' exhibits excellent optical compensation ability. Further, the optical characteristics of the optically anisotropic layer 12' are adjusted such that the front retardation Re(Re) is not 0, and the optical compensation sheet which is the tilt axis (rotation axis) in the in-plane slow phase axis is used. The normal direction, the hysteresis 测定 measured when the light of the wavelength ληηι is incident in a direction inclined at +40°, and the optical compensation ♦ the relative axis with respect to the in-plane slow axis (rotation axis) In the normal direction, the hysteresis 测定 measured when the light of the wavelength ληπι is incident at an oblique angle of -40° is substantially equal, so that the liquid crystal cell, especially the liquid crystal cell of the V Α mode, can be correctly compensated. Further, "positive retardation (Re) is not 0" means that Re is not less than 3 nm. [Polarizing Plate] Figs. 3(a) to (d) are schematic cross-sectional views of a polarizing plate having an optical compensation sheet according to the first or second aspect of the present invention. The polarizing plate can be generally produced by dyeing a polarizing film made of a polyvinyl alcohol film with iodine, stretching to obtain a polarizing film ® 21, and protecting the films 22 and 23 in two areas thereof. Since the optical compensation sheet of the first or second aspect of the present invention has a support formed of a polymer film or the like supporting the optically anisotropic layer, the support can be used as it is at least one of the protective films 22 and 23. By. In this case, the optical anisotropic layer 12 (or 12') may be disposed on the side of the polarizing layer 21 (ie, the optically isotropic layer 12 (or 12') is closer to the polarizing layer 21 than the support 11), It may be disposed on the opposite side from the polarizing layer 21 (ie, the optically isotropic layer 12 (or 12') is farther away from the polarizing layer 21 than the supporting layer), but as shown in Fig. 3(a) The directional layer 1575093 12 (or 12') is preferably on the opposite side to the polarizing layer 21. Further, as shown in Fig. 3 (b), the outer side of one of the protective films 22 of the polarizing layer 21 may be bonded via an adhesive or the like. The third (c) and (d) diagrams are examples of the structure of the polarizing plate in which the other functional layer 24 is disposed on the polarizing plate of the structure shown in Fig. 3(a). The third (c) is a configuration example in which the other functional layer 24 is disposed on the protective film 23 disposed on the opposite side of the optical compensation sheet and the polarizing layer 2 of the first or second aspect of the present invention. The third (d) is a structural example in which the other functional layer 24 is disposed on the optical compensation sheet ♦ of the first or second aspect of the present invention. The example of the other functional layer is not particularly limited, and for example, it can be a functional layer which imparts various characteristics to a λ/4 layer, an antireflection layer, a hard coat layer or the like. These layers are used as one of a λ/4 plate, an antireflection film, a hard coat film, and the like, and may be bonded, for example, by an adhesive. The configuration example of the third (d) diagram can form the other functional layer 24 and the polarizing layer 21 on the optical compensation sheet (optical anisotropic layer 12 or 12') of the first or second aspect of the present invention. Made with fit. Further, the protective film 23 on the opposite side of the optical compensation sheet of the first or second aspect of the present invention may itself be a functional film such as a λ/4 plate, an antireflection film or a hard coat film. When a polarizing plate is produced by laminating a polarizing film and a protective film, a total of three films of a pair of protective films and a polarizing film can be bonded by a roll-to-roller. This roll-to-roll method is a preferred method of producing a polarizing plate not only from the viewpoint of productivity, but also because the polarizing plate is less likely to undergo dimensional change or curling and imparts high mechanical stability. [Liquid Crystal Display Device] Fig. 4 is an example of a liquid crystal display device of the present invention. The liquid crystal display device 1475093 has a pair of polarizing plates 36 sandwiched between the upper and lower electrode substrates, and a pair of polarizing plates 36 disposed on both sides of the liquid crystal cell, and the other one uses the polarizing plate of the present invention shown in FIG. In the case of the polarizing plate, the optically anisotropic layer is disposed so as to be between the polarizer-electrode substrates. The alignment liquid crystal is applied to the alignment layer on the electrode substrate and the surface thereof is provided with a structure such as a rib, and is controlled so as to be predetermined to the lower side of the liquid crystal cell held by the polarizing plate. • A dimming film 34 such as a brightness enhancement film or a diffusion film. On the lower side, in order to illuminate the reflecting plate 32 and the light guide plate 33 from the light emitted from the cold cathode tube 31. In place of the cold cathode tube and the backlight unit, there is also a direct-type backlight in which a plurality of cold cathode tubes are arranged, or an LED is used as a light source. g is a surface-emitting optical film using organic EL, inorganic EL or the like. Any kind of backlight has an effect. Further, although not shown in the drawings, in the reflective liquid crystal ®, the polarizing plate may be disposed on the observation side only one piece, and the reflection film may be provided on the inner surface of the lower substrate of the liquid cell. Of course, the front light of the light source is disposed on the viewing side of the liquid crystal cell. Further, the inside of the pixel may be a semi-transparent having a transmissive portion and a reflecting portion. Next, a material, a production method, and the like used for the production of the first and second sheets of the present invention will be described in detail. The first and second aspects of the present invention (hereinafter, particularly indicated in the present invention, it is intended to include the first and second liquid crystal cells 3, 37, and the polarizing plate to: use the optical layer of the present invention The sub-system of the liquid crystal cell is provided by the rubbing treatment or the alignment state of the liquid crystal cell. The one having the one or more is placed on the front side of the light-adjusting film, and the light-guiding plate is formed below the liquid crystal cell. LED backlight, or light, but the back surface or liquid of the aspect cell of the display device of the present invention may also use the above-mentioned image type of the display device. In the case of optical compensation of the aspect, if there is no dream or sample The -19- 1375093 optical compensation sheet has a transparent support, the above polymer layer, and the optically different directional layer, wherein the optical anisotropic layer is used to expand the contrast angle of the liquid crystal display device and eliminate the liquid crystal display. The portrait of the device is colored. In the optical compensation sheet of the present invention, the support of the optically anisotropic layer serves as a protective film for the polarizing plate, or the optical anisotropic layer serves as a protective film for the polarizing plate, thereby reducing liquid crystal display. The components of the device. That is to say, in such a manner, the thickness of the liquid crystal display device is also reduced. In the present invention, liquid crystal display can be remarkably improved by forming an optically anisotropic layer formed of a liquid crystal compound on an optically monoaxial or biaxial transparent m support formed of a polymer. Optical properties of the device. [Optical anisotropic layer formed by liquid crystal compound] In the present invention, as described above, the optically anisotropic layer formed by curing a liquid crystal layer containing a liquid crystal compound contributes to optical compensation of a liquid crystal cell. It is of course possible to have a state in which the optically anisotropic layer alone has sufficient optical compensation energy' and also to combine with other layers (e.g., a support) to satisfy the optical characteristics required for optical compensation. The above optically anisotropic layer ® is formed of a composition containing at least one liquid crystal compound. In general, liquid crystal compounds can be classified into a rod shape and a disk shape depending on the shape of their molecules. Furthermore, each has a low molecular type and a high molecular type. Polymers generally refer to those with a degree of polymerization of more than 100 (polymer physics. Phase transfer kinetics, Doi Masaru, 2 pages, Iwabo Bookstore, 1 9 9 2). In the present invention, any liquid crystal compound may be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystal compounds, two or more kinds of discotic liquid crystal compounds 'or a mixture of a rod-like liquid crystal compound and a discotic liquid crystal compound may be used. Since (S) -20 - 1375093 can be changed in temperature or humidity, the formation of a rod-like liquid crystal compound or a discotic liquid crystal compound having a reactive group is more preferable, and in the case of a mixture, at least one is 1 There are two reactive groups in the liquid crystal molecule which are particularly excellent. Liquid crystal • The compound may be a mixture of two or more kinds. In this case, at least one reactive group having 2 or more is preferred. The thickness of the above optically anisotropic layer is preferably from 0.1 to 20 μm, more preferably from 0.5 to ΙΟμηη. As the rod-like liquid crystal compound, it is preferred to use a subliminal limb, an oxidized azo 'based 'cyanobiphenyl, a cyanophenyl ester, a benzoate, a cyclohexane carboxylic acid phenyl ester, Cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, diphenylacetylenes, and alkenylcyclohexylbenzonitriles. Not only the above low molecular liquid crystal compound but also a polymer liquid crystal compound can be used. The polymer liquid crystal compound is a polymer compound obtained by polymerizing a rod-like liquid crystal compound having a low molecular reactivity group. The above-mentioned rod-like liquid crystal compound having a low molecular reactivity group to be used is a rod-like liquid crystal compound represented by the following formula (IV). _ General formula (IV): Q1 - Ι^-Α1 - L3-M-L4-A2-L2-Q2 where Q1 and Q2 are each independently a reactive group, and L1 'L2, L3 and L4 are each independently Represents a single bond or a divalent linker, but at least one of L3 and L4 represents -0-, -0-C0-'-C0-0- or -0-C0-0-. A1 and A2 each independently represent a spacer having 2 to 20 carbon atoms. Μ denotes an intermediate (!^5011§611) base β or less, and a rod-like liquid crystal compound having a reactive group represented by the above formula (IV) will be described in more detail. In the formula, the polymerization reaction of each of the reactive groups of Q1 and Q2 is preferably an addition polymerization (including ring-opening polymerization) or a condensation polymerization. In other words, the reactive group is preferably a reactive group which can be subjected to addition polymerization or condensation -21 - 1375093 polymerization. Examples of reactive groups are shown below. 【化7】 Η Η h3c,c^c^ Η Η

Et 'C* Η Η n.Pr, c々C, Η CHa h2c^c,

Cl

Η

Ο Ν

HjC-CH^ H2C-CH^ —SH —OH —NH2 N=Cs〇

—I is a divalent linking group represented by L1, L2, L3 and L4, preferably selected from the group consisting of -Ο-, -S-, -CO-, -NR, ·-CO-0-, -O-CO -O-, -CO-NR2-, -NR2-CO-, -O-CO-, -O-CO-NR2-, -NR2. . -. - and • The divalent linking group of the group consisting of NR2-CO-NR2-. The above R2 is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In the above formula (IV), (^-1^ and Q2-L2- are preferably ch2 = ch-co-o-, CH2 = C(CH3)-C0_0-, and CH2 = C(Cl)-C0-0 -C0-0-, more preferably ch2 = ch-co-o-. A1 and A2 represent a spacer having 2 to 20 carbon atoms, preferably an aliphatic group having 2 to 12 carbon atoms. The alkyl group is preferably a chain-like group which also contains an oxygen atom or a sulfur atom which is not adjacent. Further, the above spacer may have a substituent of 8-22 to 1375093, which may be a halogen atom (fluorine, chlorine 'bromine And an intermediate group represented by Μ, for example, may be any conventional intermediate group, and particularly preferably a group represented by the following formula (V). ): - (- W1- L5)n- W2- where 'W1 and W2 each independently represent a divalent cyclic aliphatic group, a divalent aromatic group or a divalent heterocyclic group, and L5 represents a single bond Or a linking group. Specific examples of the linking group are specific examples of the group represented by L1 to L4 in the above formula (IV), -CH2-O- and -O-CH2-. η represents 1, 2 or 3. W1 and W2 is, for example, 14-cyclohexanediyl' fluorene, 4-phenylene, pyrimidine, 2,5-diyl, fluorene-steep-2,5-diyl, 1 ,3,4-thiadiazepine-2,5-diyl, 1,3,4-oxadiazolyl-2,5-diyl, naphthalene-2,6-diyl, naphthalene-anthracene, 5-di a group, a thiophene-2,5-diyl group, a hydrazone-3,6-diyl group. In the case of a 1,4-cyclohexanediyl group, a structural isomer of a trans form and a cis form can be any The isomer may be more preferably a mixture of β-trans system in any ratio. Wi and W2 may each have a substituent. The substituent is, for example, a _ atom (fluorine, chlorine, bromine, iodine) or a cyano group. An alkyl group (methyl group, ethyl group, propyl group, etc.) having 1 to 10 carbon atoms, an alkoxy group having a carbon number of 丨~(7) (methoxy group, ethoxy group, etc.), and 1 to 1 carbon atom a mercapto group (carbenyl group, ethyl hydrazide group, etc.), an alkoxycarbonyl group having a carbon number of 1 to 1 fluorene (methoxycarbonyl group, ethoxycarbonyl group, etc.), a decyloxy group having 1 to 10 carbon atoms (acetamidine) Alkoxy, propyloxy, etc.) 'nitro group, trifluoromethyl group, difluoromethyl group, etc.. Preferably, the basic skeleton of the intermediate group represented by the above formula (v) is not preferred. Substituted by the above substituents. [Chemical 8] 8 -23 - 1375093

Examples of the compound represented by the above formula (IV) are shown below, but the present invention is not limited thereto. Further, the compound represented by the formula (IV) can be synthesized by the method described in JP-A-11-513019. 1375093

8 -25 - 1375093 【化1〇】1-8 ΟV^c ch3 ο. Ύ

ο people CH3 〇, ο 1-9 <γΑ〇^^-〇γ〇 Ο

CI

ο ο α ο ο 1-10 ^Χ〇Α〇Ηύβ—〇

Ml '〇ΑΧΧ,° 〇Α0. •(CHzJs〆 Ο Ο M3 must be a XXJ" 1Ά 1-12 —0

(CH2)2. r°Y^

r-H 〇

r XXL CHa m〇xn^Vxxx eight eight a 1-15 〇

Ch3" Each kA 〇 0 °T〇Ol〇^ r -26 - 1375093 【化1 1】

(LC- 1-1) 8 -27 - 1375093

Ch2 two CHCOO-(CH2)6-〇

C3h7 (LC- 1- 2)

〇(CH2)6OC〇-CH=CH2

COO(CH2)4〇C〇-CH=CH2 • Examples of the discotic liquid crystalline compound which can be used in the present invention include various literatures (c. Destrade et al., Mol. Crysr. L) q. Cryst., Book 71, Dijon] 1 page (1 9 8 1); edited by the Chemical Society of Japan, Quarterly Chemistry General, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 1, Section 2 (1 994) B. Kohne et al., Angew. Chem. Soc. Chem. Comm., p. 1794 (1 985); J. Zhang et al., J. Am. Chem. Soc. 116, p. 2655 • (1994 The compound described in the above) is preferably a discotic liquid crystal compound having a triphenylene skeleton. The polymerization of a discotic liquid crystal compound is described in JP-A-8-2728. The discotic liquid crystalline compound preferably has a reactive group and can be fixed by polymerization. For example, a structure in which a disc-shaped center ' of a discotic liquid crystalline compound is bonded to a reactive group as a substituent may be considered, but when the disc-shaped center is directly bonded to a reactive group, the alignment system is preserved during the polymerization reaction. Have difficulty. Therefore, it is preferable to have a structure having a linking group between the center of the disk and the reactive group. That is, a discotic liquid crystalline compound having a reactive group, 8-28 - 1375093 is preferably a compound represented by the following formula (VI). 'Formula (VI) ·· D(- L— P)n where D is a discotic center, L is a divalent linking group, p is a reactive group, and η is an integer of 4 to 12. • Preferred specific examples of each of the disc-shaped center (D), the divalent linking group (L), and the reactive group (Ρ) in the above formula (VI), for example, the special opening 2 00 1 - 4 83 In the publications (D1) to (D15), (L1) to (L25), and (Ρ1) to (Ρ18) described in the publication No. 7, the divalent linking group (L) described in the publication can be preferably used. Reactive ® based (Ρ) content. Further, the discotic liquid crystalline molecule is also preferably a photosensitive functional group.

I Photosensitive functional groups can initiate reactions by light (see Science of Optical Functional Molecules, Chapter 2, Handcrafted, Niu Muxiu, Lecture, 992). The reaction includes cleavage of a sigma bond, a reaction of a C=C double bond, and a reaction of a C=0 double bond. The refractive index of the discotic liquid crystalline molecule is preferably changed by the reaction. Therefore, the cleavage of the sigma bond or the reaction of the C=C double bond is preferred, and the reaction of C=C double bond ® is particularly preferred. The C=C double bond is preferably conjugated to the benzene ring. The double bond conjugated to the benzene ring dimerizes by forming a 4-membered ring between the two molecules by light irradiation. Thereby, the refractive index of the discotic liquid crystalline molecule is changed. Particularly preferably, the discotic liquid crystalline molecule has a substituent having a benzene ring and a valence group of a double bond which is lightly bonded to the benzene ring as a discotic core. Preferably, the benzene ring and the double bond conjugated to the benzene ring are contained between the discotic core of the discotic liquid crystalline molecule and the reactive group. The discotic liquid crystalline molecule represented by the following formula (VI1) is particularly preferable. [化1 3] -29 - 1375093

In the formula (VII), A1 is CX1 or N. The CX1 system is better than N. X 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. X1 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 9 to 3 carbon atoms. , the best hydrogen atom. In formula (VII), A2 is CX2 or N•. The CX2 system is better than N. X2 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, or is bonded to Y to form a 5-membered ring or a 6-membered ring. X2 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Good hydrogen atom. In the case where the ring formed by X 2 and Y is bonded, the hydrocarbon ring system is more preferable than the hetero ring, and the aliphatic ring system is more preferable than the aromatic φ group ring. Further, the 6-membered ring system is more preferable than the 5-membered member. In the formula (VII), a Y-based hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a carbon atom. The fluorenyl group having 2 to 13 carbon atoms, the alkylamino group having 1 to 12 carbon atoms or the decyloxy group having 2 to 13 carbon atoms may be bonded to X2 to form a 5-membered ring or a 6-membered ring. Y is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Good hydrogen atom. In the formula (VII), a Z-based halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorenyl group having 2 to 13 carbon atoms, and a carbon number of 1 to 12 CS) An alkylamino group of -30 to 1375093 or a decyloxy group having 2 to 13 carbon atoms. Z is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a group having 1 to 3 carbon atoms. In the formula (VII), L1 is selected from the group consisting of -O-, -CO-, -S-, -NH, alkylene, alkenyl, extended aryl, extended aryl and combinations thereof. base. The divalent linking group formed by this combination is exemplified below. The left side is bonded to the benzene ring, and the right side is bonded to the reactive group (Q). AL means an alkyl group, an alkenyl group or an alkynyl group, and AR means an aryl group.

1: an AL — C 0 — Ο an AL — 2: — AL — CO — Ο — AL — Ο a 3 : — AL — CO — Ο — AL — Ο an AL — 4 : an AL — CO _ 0 — AL — Ο — CO — 5 : — C Ο — AR — Ο — AL — 6: — CO — AR — Ο an AL — Ο a 7: — CO — AR — Ο an AL — O _ CO — 8: — CO- NH-AL — 9 : An NH- AL- Ο — 10 : - ΝΗ- AL- Ο- COL-1 1 : One Ο — AL- L A 12: — O a AL — Ο — L - 1 3 : - O -AL-O—CO-L-14: _ O_AL — O—CO — NH — AL _ L — 15: — O — AL — S — AL — L- 16 : An O-CO-AL-AR — O-AL-O-CO — • 3 1 - 8 1375093 L-17: - O-CO- AR- O-AL- CO-L-18: - 〇- CO - AR - O - AL - O - CO— L - 19: - O- CO-AR— 0— AL-O-AL-O-CO-L 2〇: 一〇—CO _ AR — O — AL _ 0 _ AL — O - AL — 〇 — CO ~ L-2l: - S - AL -L-22: - S - AL - O -L- 23 : -S-AL-O-CO-L _ 24 : — S _ AL — S _ AL —

L ~ 2 5 : — S-AR-AL- In the formula (VII), L2 is a single bond or a 1,4-phenylene group. A single bond is preferably 1,4-phenylene. In the formula (VII), the Q is a reactive group. The reactive group (Q) is determined depending on the type of the polymerization reaction. An example of the reactive group (Q) is shown below. (Q1) (Q2) (Q3) (Q4) -CH=CH2 -CH=CH-CHa -CH=CH-C2Hs -CH=CH-n-C3H7 [Q5) (Q6) (Q7) ( Q8) (Q9) (Q10) — C=CHa —ch=c-ch3 —cech oh —sh ch3 ～ -ch-ch2 (Qll) (Q12) (Q13) (Q14) (Q15) (Q16) (Q17)

—CHO —OH —C02H —N=G=Q —NH 2 —S03H —N=G=S The reactive groups (Q 1 and Q 2 ) are preferably unsaturated reactive groups (Q −1 to Q -7), The epoxy group (Q-8) or azacyclopropyl (Q-9)' is more preferably an unsaturated reactive group, and most preferably an ethylenically unsaturated reactive group (Q-1 to Q-6). In the formula (vii), a is 1, 2, 3 or 4. a is preferably 1, 2 or 3, more preferably 1 or 2, and particularly preferably 1. In the case where a is 1, -L1 - Q is preferably bonded to the 4th position of the benzene ring. In the formula (VII), 'b is 0, 1, 2 or 3. b is preferably 0 (§) -32-1375093, 1 or 2, more preferably 0 or 1, especially good. In the formula (VII), a + b is 1, 2, 3 or 4. The six R's in the formula (VII) may be different, but are preferably the same. Hereinafter, an example of a discotic liquid crystalline molecule represented by the formula (νπ) will be represented by R. [化1 5]

An example of the optically anisotropic layer may be a molecule having a rod-like liquid crystal compound having a reactive group on the polymer layer of less than 5. After the cholesteric alignment of the average tilt angle, the polarized light is irradiated to simultaneously perform the optical biaxial display and the polymerization of the molecules of the liquid crystal compound. In the case of using a rod-like liquid crystal compound having a reactive group, it is necessary to illuminate the cholesteric alignment system for exhibiting biaxiality by polarized light. As a method of aligning the skew by the polarized light, for example, a method using a dichroic liquid crystalline polymerization initiator (International Publication No. WO 3 0 / 5 5 4 1 1 1) or using a cinnamyl group in the molecule is used. A method of a rod-like liquid crystal compound of a photo-alignment functional group (JP-A-20-2). Another example of the optically anisotropic layer may be a molecule having a discotic liquid crystal compound having a reactive group on the polymer layer of less than 5. After the alignment of the average tilt angle, the polarized light is irradiated to simultaneously perform the optical biaxiality and the polymerization of the molecules of the above liquid crystal compound. -33 - 1375093 In the case of using a discotic liquid crystal compound having a reactive group, it may be fixed in any of an alignment state, a vertical alignment, and a twist alignment, but is preferably symmetrical with respect to a normal direction of the film. More preferably for horizontal alignment. Horizontal alignment means that the disc surface at the center of the discotic liquid crystal compound is parallel to the horizontal surface of the transparent support body, but does not require strict parallelism. In this specification, it means an alignment with a slope angle of less than 10°. , especially good for less than 5. 〇 ' The front side retardation (Re) of the optically anisotropic layer is not zero. Re non-〇 ® means that Re is not less than 3nm. Re is preferably from 3 to 250 nm, more preferably from 7.5 to 100 nm, particularly preferably from 15 to 80 nn, and the total of Rth % of the transparent support is preferably from 30 to 500 nm, more preferably from 40 to 400 nm, particularly preferably 1 In the case where the optically anisotropic layer formed of the liquid crystal compound is formed by laminating two or more layers, the combination of the liquid crystal compounds is not particularly limited, and may be completely composed of a discotic liquid crystal compound. A layered body of the layer formed, a layered body of a layer entirely composed of a rod-like liquid crystal compound, a layer formed of a layer of a discotic liquid crystal compound, and a layer of a layer made of a rod-like liquid crystal compound. Further, the combination of the alignment states of the respective layers is not particularly limited, and may be an optically anisotropic layer in which the layers are in the same alignment state, or may be an optically anisotropic layer in which different alignment states are laminated. The optically anisotropic layer is preferably formed by coating a coating liquid containing a liquid crystal compound and a polymerization initiator described below and other additives on the alignment layer. The solvent used in the preparation of the coating liquid is preferably an organic solvent. Examples of the organic solvent include guanamines (for example, dimethylformamide), yttrium 1575093 (for example, dimethyl sulfite), and heterocyclic compounds (for example). For example, pyridine), hydrocarbons (such as benzene, hexane), alkyl halides (such as chloroform, dichloromethane), esters (such as methyl acetate, butyl acetate), ketones (such as acetone, methyl ethyl) Ketone), ethers (for example, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. It is possible to use two or more organic solvents. The coating liquid can be applied by a conventional method (for example, extrusion coating, direct gravure coating, reverse gravure coating, die coating, and wire coating). Implementation. [Immobilization of alignment state of liquid crystal compound]

The aligned liquid crystalline molecules preferably maintain a fixed alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into a liquid crystalline molecule. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization is preferred. Examples of the photopolymerization initiator include a-carbonyl compounds (described in the respective specifications of U.S. Patent No. 2,376,661, No. 23,67,086), decyloxyether (described in the specification of U.S. Patent No. 2,448,082), and a-hydrocarbon substitution. Aromatic auxin compounds (described in U.S. Patent No. 2,725, 152), polynuclear ruthenium compounds (described in each specification of U.S. Patent Nos. 3,046,127 and 2,951,758), tri-p-imidazole dimers and p-aminophenyl ketones The combination (described in the specification of U.S. Patent No. 3,493,67), the acridine and the porphyrin compound (described in the specification of Japanese Patent No. 60-105667, U.S. Patent No. 423 9850) and the oxadiazole compound (US Patent No. 42) 1 2970 manual description). The amount of the photopolymerization initiator to be used is preferably from 0.01 to 20 by mass, more preferably from 0.5 to 5 by mass, based on the solid content of the coating liquid. It is preferred to use ultraviolet rays for the light irradiation required for the polymerization of the liquid crystalline molecules. The irradiation energy is preferably 20 m: f/cm 2 to 3 - 35 to 1375093 lOJ/cm 2 , more preferably 100 to 800 m J/cm 2 . In order to promote photopolymerization, light irradiation can be carried out under heating conditions. [Photoalignment due to polarized light irradiation] ' In the present invention*, the in-plane retardation of the optically different direction layer may be generated by polarized light irradiation. The polarized light irradiation may be performed simultaneously with the photopolymerization process during the alignment fixation, or may be performed by polarized light irradiation and then immobilized by non-polarized light irradiation. Alternatively, the polarized light may be fixed by non-polarized light irradiation before being polarized. . In order to obtain a large hysteresis, it is preferred to use only polarized light or the first ® polarized light. The polarized light irradiation is preferably performed at an oxygen concentration of 3 % or less, more preferably 5% or less, in an inert gas atmosphere, and particularly preferably a polarized light having a peak at 3 65 ± 10 nm, more preferably at 365 ± 5 nm. Polarized illumination with peaks. The irradiation energy is preferably from 20 mJ/cm 2 to 50 J/cm 2 , more preferably from 100 to 800 J/cm 2 . The illuminance is preferably from 20 to 10 00 mW/cm 2 , more preferably from 50 to 50,000 Mw/cm 2 , and particularly preferably from 10 0 to 3 5 0 m W / c m 2 . The type of the liquid crystalline compound which is cured by polarized light irradiation is not particularly limited, and a liquid crystalline compound having a reactive group and an ethylenically unsaturated group is preferred. Further, the optical anisotropic layer for displaying the in-plane retardation due to the light alignment by the polarized light irradiation is particularly excellent in the optical compensation VA mode liquid crystal display device. [Horizontal alignment agent] The second aspect of the present invention is a composition containing a liquid crystal compound and a fluorine-containing level alignment agent in the composition for forming an optically anisotropic layer. In the first aspect of the present invention, a liquid crystal compound and a fluorine-containing horizontal alignment agent may be contained in the composition for forming an optically anisotropic layer. By using one of the fluorine-containing horizontal alignment agents to less than 8 - 36 - 1375093, the molecules of the liquid crystal compound can be substantially horizontally aligned to form an optically anisotropic layer having uniform optical characteristics. Further, the above-mentioned fluorine-containing horizontal alignment agent also contributes to alleviation of unevenness of the film surface. Further, in the present invention, the "horizontal alignment" means that in the case of a rod-like liquid crystal, the long axis of the molecule is parallel to the horizontal plane of the transparent support, and in the case of a discotic liquid crystal, it means a discotic liquid crystal. The disc face of the center of the compound is parallel to the horizontal plane of the transparent support and does not require tight parallelism. In the present specification, it means an aligner having an inclination angle of less than 10 degrees with the horizontal plane. The tilt angle is preferably 〇~5 degrees, more preferably 0~3, degrees 'special 〇~2 degrees, best 〇~! degree. The fluorine-containing horizontal alignment agent is preferably a disk-shaped compound represented by any one of the following formulae (Ι) to (ΠΙ). The general formulae (1) to (111) will be described below. [Chemical Formula 1] General Formula (I) R1\

R2 wherein R1' and R3 each independently represent a hydrogen atom or a substituent, and at least - X1, X2 and X3 represent a single bond or a divalent group of substituents representing a fluorine atom, and a substituent. [Chemical 1 7] General formula (II)

24 R 24 R R , R: R22, R23, R24 and R25 each independently represent a hydrogen atom or a substituent representing a fluorine atom;

, the compound represented by the formula (ί). The substituents represented by R1, R2 and r3 include, for example, an alkyl group (preferably an alkyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms). , for example, methyl, ethyl, isopropyl, tert-butyl 'n-octyl'-n-decyl, n-hexadecanyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl (preferably carbon) 2 to 40, more preferably 2 to 30 carbon atoms, particularly preferably an alkenyl group having 2 to 20 carbon atoms, such as a vinyl group, an allyl '2-butenyl group, a 3-pentenyl group, etc.), an alkynyl group (compared Preferably, the carbon number is -38 - 1375093 2 to 40, more preferably a carbon number of 2 to 30, a particularly preferred alkynyl group having a carbon number of 2 to 20, such as propynyl or 3-pentynyl, or an aryl group (preferably An aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, a naphthyl group or the like, a substituted or substituted amino group (preferably, It is an amine group having a carbon number of 0 to 40, a more preferable carbon number, 〇30, and a carbon number of 0 to 20, for example, a substituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, an anilino group, or the like. ), alkoxy (preferably carbon number 1 to 40, more preferred carbon number 1 to 30, particularly good carbon number 1 dream ~ 2 〇 An oxy group, for example, a methoxy group, an ethoxy group, a butoxy group or the like), an aryloxy group (preferably having a carbon number of 6 to 40, a more preferred carbon number of 6 to 30, and a particularly preferred carbon number of 6 to 20) An oxy group such as a phenoxy group, a 2-naphthyloxy group or the like, a fluorenyl group (preferably a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, and a particularly preferred carbon number of 1 to 20, such as B) Anthracenyl, benzhydryl, methionyl, trimethylethenyl, etc.), alkoxycarbonyl (preferably having a carbon number of 2 to 40, more preferably a carbon number of 2 to 30, and a particularly preferred carbon number of 2 to 20) An alkoxy group [e.g., methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having a carbon number of 7 to 40, more preferably a carbon number of 7 to 30, and a particularly preferred carbon number of 7 to 20, for example, Phenoxycarbonyl or the like] 'decyloxy (preferably a carbon number of 2 to 40, more preferably 2 to 30 carbon atoms, and a particularly preferred carbon number of 2 to 20 carbon atoms) such as an ethoxy group or a benzepoxide And the like; amidino group (preferably having a carbon number of 2 to 40', preferably a carbon number of 2 to 30, and a particularly preferred carbon number of 2 to 20, such as an acetamino group, a benzylamino group, etc. Alkoxycarbonylamino group (preferably alkoxycarbonylamino group having a carbon number of 2 to 40, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 20 carbon atoms) 'E.g. methoxycarbonylamino group, etc.' 'Aryloxycarbonylamino group (preferably an aryloxyamino group having a carbon number of 7 to 40, more preferably a carbon number of 7 to 30, and a particularly preferred carbon number of 7 to 20, such as benzene) Oxycarbonylamino group, etc., sulfonamide group (preferably carbon number! ~ 1375093 4〇, more preferably 1 to 30 carbon atoms, particularly preferably a carbon number of 1 to 20, such as methyl 'sulfonamide Base, benzenesulfonylamine, etc.), sulfonamide (preferably carbon number 〇~40, more preferably carbon number 〇30), particularly good carbon number 〇~2〇, amine sulfonyl group, such as 'amine expansion Sulfhydryl, methylamine sulfonyl, dimethylamine sulfonyl, phenylamine sulfonyl, etc.) • Aminomethyl thiol (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30) Particularly preferred is an aminomethyl group having 1 to 20 carbon atoms, such as an unsubstituted amine methyl sulfonyl group, a methylamine methyl fluorenyl group, a diethylamine methyl fluorenyl group, a phenylamine methyl fluorenyl group, etc., a decylthio group. (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, a particularly preferable carbon number of 1 to 20', for example, a phenylthio group, etc.), a sulfonyl group (preferably a carbon number) of 40 or more. a sulfonyl group having a carbon number of 1 to 30 and a particularly preferred carbon number of -20, such as a methylsulfonyl group or a toluene group, etc.) a sulfonyl group (preferably a sulfinyl group having a carbon number of 1 to 40, more preferably 1 to 3 carbon atoms, and a particularly preferred carbon number of 1 to 20, such as a sulfinyl group, a sulfinyl group, etc.), a ureido group (preferably a ureido group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, such as an unsubstituted ureido group, a methylureido group, a phenylureido group, etc.), Phosphoric acid amine group (preferably having a carbon number of 1 to 40, more preferably 1 to 30 carbon atoms, and particularly preferably having a carbon number of 1 to 20, such as diethylphosphonium amide, phenyl I guanamine phosphate Base, etc.), hydroxyl group, thiol group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfonic acid group, carboxyl group, nitro group, hydroxamic acid group, sulfinic acid group, A mercapto group, an imido group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom) Imidazolyl, pyridyl 'quinolinyl, fluorenyl, piperidine, morpholinyl, benzoinyl, benzimidyl, benzothiazolyl, 1,3,5-three tillage, etc.) , decyl alkyl (preferably carbon number 3 to 4 〇, better carbon The number is preferably from 3 to 30, particularly preferably a decyl group having a carbon number of from 3 to 24, such as trimethyldecyl 3-40- 1375093, triphenyl sand, etc.). These substituents may also be substituted by these substituents. Further, in the case of having two substituents, they may be the same or different. Moreover, where possible, they may be combined to form a loop. In the above, the substituent represented by each of the formulas ... and r3 is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. At least one of R1, R2 and R3 represents a substituent of a fluorine atom. The substituent represented by each of R1, R2 and R3 may have a substituent other than a fluorine atom, and the substituent is preferably an alkyl group, an aryl group, a substituted or substituted amino group 'alkoxy group, ^ thiol group or The _ atom is more preferably a fluorine atom. Namely, R1, R2 and R3 are preferably each a substituent having a fluorine atom. The divalent linking group represented by X, X and X3 is preferably selected from the group consisting of an alkyl group, an alkenyl group, a divalent aromatic group, a divalent heterocyclic residue, _co_, and -NRa- (Ra). An alkyl group having 1 to 5 carbon atoms or a hydrogen atom), -〇_, -S·, -SO-, -SO2-, and a divalent linking group of the group formed by these combinations. The divalent linking group is more preferably a divalent linkage selected from the group consisting of an alkyl group, *S'-C0-, -NRa-, -0-, -S-_, -S〇2_, and the like. At least two of the groups are combined. The number of carbon atoms in the stretching base is preferably from 1 to 12. The number of carbon atoms of the alkenyl group is preferably from 2 to 12. The number of carbon atoms of the divalent aromatic group is preferably from 6 to 10. The alkyl group, the alkenyl group and the divalent aromatic group may, if possible, be represented by the substituents of the above R1, R2 and R3 (for example, an alkyl group, a halogen atom, a cyano group, an alkoxy group, a decyloxy group). ) replaced by. Among the compounds represented by the above formula (I), a compound represented by the following formula (Ia) or (lb) is particularly preferred. [I 9] -41- 1375093 General formula (la)

In the formula, Rla, R2a and Rh each represent a hydrogen atom or a substituent, and at least one of them represents a substituent of a fluorine atom. Xla, 乂28 and 乂33 each represent -NH-, -〇. or -S-, and mla, m2a and m3a represent integers of 1 to 3.

[Chem. 20] Formula (lb)

Wherein Rf1, Rf2 and Rf3 represent an alkyl group having a CF3 group or a cf2H group at each terminal, and Y1, Y2 and Y3 are represented by an alkyl group, -CO-, -NH-, (;)., -S-, -SOz- and a group of at least two of the divalent linking groups selected by the population of such groups. First, the compound represented by the formula (T a) will be explained.

The respective substituents represented by Ru, R28 and R3a are synonymous with R1, R2 and R3 in the above formula (1), and the preferred ranges thereof are also the same. The substituents represented by Rla, R2a and R3a are particularly preferably those having a CF3 group or a CF2H group at the terminal. The alkyl chain contained in the alkoxy group may be linear or branched, and preferably has a carbon number of 4 to 20, more preferably 4 to 16 carbon atoms, and particularly preferably 6 to 16. The alkoxy group having a CF3 group or a CF2H group at the terminal end is an alkoxy group which is one or both of hydrogen atoms 42 to 1375093 atoms contained in the alkoxy group. The hydrogen atom in the alkoxy group is preferably 50% or more by a fluorine atom, more preferably 60% or more by a fluorine atom, and particularly preferably 70% or more by a fluorine atom. Examples of the alkoxy group having a CF3 group or a CF2H group at the terminal represented by Rla, R2a and R3a are shown below. R1 : η — C 8 F 17 — 〇 — R2 · η — C 6 F 13 — 〇 — continued R3 * η - C4F9 — 0 — , R4: n- C8F】7- (CH2) 2-0-(CH2) 2- 〇-R5 : π — C 6 F 1 3 " ( c Η 2 ) 2 — 0 — ( CH2 ) 2 — 0 — 磉R6: n — C4F9- (CH)) 2 - 〇— (CH2) 2 *~〇— R7 * η — C 8 F 17 ( C Η 2 ) 3 〇 — R8: n — C6Fi3_ ( C Η 2 ) 3 — Ο ~~ R9. n — C 4 F 9 —(CH2) 3 — Ο — R,u : H - ( cf2 ) 8 — 0 — — R11 : H — ( cf2 ) 6 — 0 — R12 H — ( cf2 ) 4 — 0 — R13 H — ( cf2 ) 8 — ( ch2 ) —0 — R14 H - ( cf2 ) 6 — ( ch2 ) -0 - R15 H - ( cf2 ) 4 — ( ch2 ) —0 A R1 6 H- ( cf2 ) 8 — ( ch2 ) -0 - ( ch2 ) 2 — 0 - R17 H - ( cf2 ) 6 — ( ch2 ) - 0 - ( ch2 ) 2 — 0 — R1 8 : H- ( cf2 ) 4 — ( ch2 ) -0 - ( ch2 ) 2 — 0 —

Xla, X2a and X3a each preferably represent -NH- or -0-, more preferably -NH-43-1375093. Mla, m2a and m3a are each preferably 2. * Next, the compound represented by the formula (rb) will be explained.

The *alkyl group having a CF3 group or a CF2H group at the terminal represented by Rfh Rf2 and Rf3 may be linear or branched, preferably having a carbon number of 4 to 20'. More preferably carbon number * 4 to 丨6, Good 6 to 16. It may have a substituent other than the CF3 group or the CF2H group. The alkyl group having a CF3 group or a CFaH group at the terminal is an alkyl group which is contained in the alkyl group and which is partially or wholly substituted by a fluorine atom. The y hydrogen atom in the alkyl group is preferably 50% or more substituted by a fluorine atom, more preferably 60% or more by a ® fluorine atom, and particularly preferably 70% or more by a fluorine atom. Examples of the hospitaloxy group having a CF3 group or a CF; jH group at the terminal represented by Rf1, Rf2 and Rf3 are shown below.

Rf,: n- C8F17-

Rf2 : n- C6F13-

Rf3 · · n - C4F9 -

Rf4 : n- C8F17- (CH2)2-

Rf5 : n- C6FI3_ (CH2)2-

Rf6 : n - C4F9_ (CH2)2 -

Rf? : H- (CF2)8-

Rf8 : H- (CF Mountain -

Rf9 : H- (CF2)4-

Rf10 : H - (CF2)8 - (CH2)-

Rf11 : H - (cf2)6 - (CH2) -

Rf12 : H - (cf2)4-(CH2)- γΙ ' Y2 and Y3 each preferably represent two selected from the group consisting of alkyl, -NH-, -O-, -S_ and -44 - 1375093 More preferably, the combination of at least two of the valent linking groups is -NH-, -〇- or -NH(CH2)r-〇- (an integer represented by r, preferably 3). (Π) The compound represented. In the formula (π), each substituent represented by r21, R22, r23, r24 and R25 has the same meaning as the substituent represented by R1, & 2 and r3 in the formula (I), and the preferred range thereof is also the same. m preferably represents an integer of 1 to 3, particularly preferably 2 or 3. At least one of r2i, R22, R23, R24 and R25 represents a fluorine-containing substituent. Preferably, two or three substituents of r2i, ?r22, R23, R24 and R25, more preferably ^3 substituents' are more preferably three fluorine atom-containing substituents. Among the compounds represented by the above formula (II), a compound represented by the following formula (IIa) is particularly preferred. [Chem. 2 1]

In the formula C〇2H, Rfla, Rf2a and Rf3a each independently represent an alkyl group having a CF3 group or a CFsH group at the terminal, and Yla, and each independently represent an alkyl group, -CO- '-NH-, -0-, And -S〇2- and a group of at least two of the divalent linking groups selected by the population of such groups.

The alkyl group having a CF3 group or a CF2H group at the terminal represented by Rfla, Rf2a and Rf3a has a CF3 group or CF2H at the terminal (§) -45 - 1375093 represented by Rf1, Rf2 and Rf3 in the above formula (lb). The alkyl group of the group is synonymous, and the preferred range thereof is also the same. Yla, Y2a and Y3a are synonymous with γι, 丫2 and γ3 in the above formula (Ib), and the preferred ranges thereof are also the same. More preferably, it is a group of at least two of divalent linking groups selected from an alkyl group, a fluorene group, and the like. • Finally, the compound represented by the formula (ΠΙ) is illustrated. Each substituent represented by R31, R32, R33, R34' R35 and r36 is synonymous with the substituent represented by R1, R2 and R3 in the formula (I), and the preferred range thereof is also the same. At least one of R31, R32, R33, R34, R35 and R36 represents a substituent having a fluorine atom, and preferably represents a substituent having a fluorine atom. ^ Among the compounds represented by the above formula (111), a compound represented by the following formula (Ilia) is particularly preferred. 【化22】 General formula (Ilia)

In the formula, RfMa, Rf22a, Rf33a, Rf44a, Rf55a and Rf66a each independently represent an alkyl group having a CF3 group or a CF2H group at the terminal, and Yna, Y22a, Y33a, Y44a, 丫553 and Y66a each independently represent an alkyl group, -CO-, -ΝΗ-, -ο-, -S-, -S02- and combinations of at least two of the divalent linking groups selected by the population of these groups -46-1375093"

Each of the alkyl groups represented by Rflla, Rf22a, Rf33a, Rf44a, Rf55a and Rf66a having a CF3 group or a CF2H group at the terminal has a CF3 group or CF2H at the terminal represented by Rf1, Rf2 and Rf3 in the above formula (lb). The alkyl group of the group is synonymous, and the preferred range thereof is also the same. Ylla, Y22a, Y33a, Y44a, 丫55!1 and Y66a are synonymous with Y1, Y2 and Y3 in the above formula (lb), and the preferred ranges thereof are also the same. More preferably, it is a group of at least two of the divalent linking groups selected from the group consisting of an alkyl group, an anthracene group, and the like. Specific examples of the compound represented by the above formula (I), (II) or (III) are shown below, but the compounds usable in the present invention are not limited thereto. In the specific examples described below, 'No. S-Ι~39 represents an example of a compound of the formula (I), and No. S-40 to 50 represents an example of a compound of the formula (II), No. S-51~ 59 represents an example of a compound of the formula (ΙΠ).

1375093

Compound N 〇. R1 R2 X S- 1 O (CH2) 3 (cf2) , f NH S- 2 o (ch2) 3 (cf2) 6f NH S — 3 O (CI-I2) a (cf2) 8f NH S -4 och2 (cf2) gH NH S- 5 och2 (cf2) 8h NH S — 6 o (ch2) 2o (ch2) 2 (cf2) 6f NH S — 7 o (ch2) 2o (CH2) 2 (CF2) 4f NH S-8 o (ch2) 3s (ch2) 2 (cf2) 6f NH S- 9 O (CI-I2) 3S (CHZ) 2 (CF2) 4F NH S- 1 0 o (ch2) 6s (ch2) 2 (cf2) 6f NH S-1 1 o (ch2) 6s (ch2) 2 (cf2) ,f NH S- 1 2 OC i 〇H 2 ! o (ch2) 2 (cf2) ,f NH S- 1 3 OC i 2 H 2 5 o (ch2) 2 (cf2) 4f NH S - 1 4 OCRH ! 7 〇(CH2) 2 (cf2) 6f NH S- 1 5 OC ! β H 3 3 〇(CH2) 2 (CFZ) 6f NH S- 1 6 OC ! 2 H 2 5 o (CI-I2) 2 (cf2) 6f NH S— 1 7 . o (ci-i2) 2o (ch2) (CF2) 61-I NH S - 1 8 O (CH2) 3 (CF,) 6F 〇S - 1 9 och2 (cf2) gh 〇S - 2 0 o (ch2) 2o (ch2) 2 (cf2) 6f o S - 2 1 0 (CI-I2) 3S (ch2) 2 (cf2) 6f o S - 2 2 o (ch2) zo (ch2) (cf2) 6h o S - 2 3 0 (CHZ) 3 (CF2) 6f s S - 2 4 och2 (cf2) 6h s S — 2 5 o (ch2) 2o (ch2) 2 (cf2) £fs S- 2 6 0 (CH2) 3S (CH2) 2 (CF2) f)F s S - 2 7 o (ch2) 2o (c H2) (cf2) 6h s -48 - 1375093 [Chem. 24] ^Rf

Rfv

A

Υ NV ^Rf Compound N 〇. R f Y S- 2 8 (ch2) 2 (cf2) 4f o S - 2 9 (ch2) 2 (cf2) 6f o S- 3 0 (ch2) 2 (cf2) 8f o S- 3 1 ch2 (cf2) 6h 〇S- 3 2 ch2 (cf2) 8h o S- 3 3 (ch2) 2 (cf2) 4f o (ch2) 2o S- 3 4 (ch2) 2 (cf2) 6f o (ch2) 2o S- 3 5 (ch2) 2 (cf2) 4f O (CH2) 3s S— 3 6 (ch2) 2 (cf2) 6f o (ch2) 6s S- 3 7 (ch2) 3 (CF2) 6f NH (CH2) 3〇S- 3 8 ch2 (cf2) 6h NH (CH2) 3〇S - 3 9 ch2 (cf2) 8h NH (CH2) 3〇 The left side of Y is connected to the triple well ring, the right side is Connect to Rf.

-49 - 1375093 [Chem. 2 5]

C02H

Rf compound N 〇. R f YS -4 0 (CH2) 3 (cf2) 4f o S -4 1 (CH2) 3 (cf2) 6f o S ~4 2 (ch2) 3 (cf2) 8f o S -4 3 Ch2 (cf2) 6h o S -4 4 ch2 (cf2) 8h o S -4 5 (CH2) 2 (cf2) 6f o (ch2) 2o S -4 6 (ch2) 2 (cf2) 4f o (ch2) 2o S -4 7 (ch2) 2 (cf2) 6f o (ch2) 3s S -4 8 (ch2) 2 (cf2) 6f o (ch2) 6S The left side of Y is connected to the benzene ring, and the right side is connected to Rf. . 【化26】

Rf /

Co2h Compound N o . .R f Y S -4 9 (CH2) 3 (cf2) 6f o S - 5 0 (ch2) 3 (cf2) 6f o (ch2) 2o -50 - 1375093

Compound N 〇. R f YS - 5 1 (cf2) , F (CH2) a S- 5 2 (cf2) rf (CH2) 3 S — 5 3 (cf2) rf (CH2j a S- 5 4 (cf2) bh ' ch2 S- 5 5 (CF2) rh ch2 S —5 6 (CH2) 2 (CFJ ,F (ch2) 2o S - 5 7 (CHZ) 2 (CFJ .F (ch2) 2o S- 5 8 (CH2) 2 (CF,) , F (ch2) 3s S - 5 9 (CH2) 2 (CFJ CF (ch2) 6s The left side of Y is attached to the oxygen atom, and the right side is linked to Rf.

The amount of the compound represented by the above formulas (I) to (III) is preferably 0. 0 1 to 2 0% by mass, more preferably 0 · 0 5 to 1 % by mass, particularly preferably the amount of the liquid crystal compound. 0.1 to 5 mass%. Further, the compounds represented by the above formulas (?) to (?) may be used singly or in combination of two or more. The compound having a 1,3,5-tri-trap ring represented by the above formula (I) can be easily synthesized by the method described in JP-A-2002-20363, and the formula (Π) and ( The compound represented by III) can be easily synthesized by a combination of a transalkylation reaction, an esterification reaction, an etherification reaction or the like. Further, the compound described in the specification of Japanese Patent Application No. 2003-3 3 1 2 69, and the synthesis method of these compounds are also described in the specification. [Alignment Layer] -51 - 1375093 In the present invention, a polymer layer is used as an alignment layer. In the first aspect of the present invention, from the viewpoint of the alignment characteristics of the liquid crystal in the formation of the optical anisotropic layer, a polymer layer formed by coating and drying a solution composed of a solvent having a water content of 20% or more is used. Used as an alignment layer. Moreover, it is characterized in that the alignment layer is chemically bonded to the 'optical anisotropic layer. In the second aspect of the present invention, from the viewpoint of the alignment characteristics of the liquid crystal in the formation of the optical anisotropic layer, it is preferred to use a solution composed of a solvent composition of 20% or more of water to be dried by coating and drying. In the alignment layer, when the alignment layer is chemically bonded to the optically anisotropic layer, the adhesion can be improved. For example, in the case of performing a water washing treatment or a saponification treatment, peeling or the like does not occur, and therefore it is preferable. y The polymer layer is preferably formed by a solution of a polymer having a reactive group composed of a solvent having a water content of 20% or more. The water in the solution of the above polymer is preferably 40% or more, more preferably 60% or more. The above polymer is soluble in a solvent containing 20% or more of water, and preferred examples thereof are a polyvinyl alcohol derivative, a poly(meth) acrylate derivative, or a polysaccharide. The reactive group of the above polymer is not particularly limited as long as it can be chemically bonded to the component of the optically anisotropic layer, preferably a liquid crystal compound. The reactive group of the above polymer is preferably an addition polymerizable (including ring-opening polymerization) reaction, and is preferably chemically bonded to the optically anisotropic layer by addition polymerization or ring-opening polymerization. By. Preferable examples of the reactive group of the polymer include a reactive group having an alkenyl group such as an acryloyl group, a methacryloyl group or a vinyl group, and a cyclic ether group such as an alicyclic epoxy group. A reactive group such as a cyclic sulfur or a cyclic imine. More preferred examples include an acrylonitrile group, a methacryloyl group, a vinyl group, an alicyclic epoxy group -52 - 1375093. The above optically anisotropic layer may also align a liquid crystal compound by a temporary alignment, and the alignment is performed. After being immobilized, it is transferred onto a transparent support body by using an adhesive or the like, but from the viewpoint of productivity, it is preferable to form a direct function film without transfer. [Transparent Support] As the transparent support of the optically anisotropic layer, a polymer film having a light transmittance t. 80% or more is preferably used. The thickness of the transparent support is preferably from 1 〇 to Φ 500 μηι, more preferably from 20 to 200 μηη, and particularly preferably from 35 to ΙΙΟμιη. The glass transition temperature (Tg) of the transparent support can be appropriately determined depending on the purpose of use. The glass moving temperature of the resin is preferably in the range of 70 ° C or higher, more preferably 75 ° C to 200 ° C, and particularly preferably 80 ° C to 18 (TC. If the resin is used in this range, heat resistance The property is highly balanced with the formability, so that the Re of the preferred ruthenium transparent support is preferably adjusted within the range of -200 to 100 nm, and Rth is in the range of -100 to 1 〇〇 nm. Preferably, it is _50~30nm, particularly preferably -30~20nm. The birefringence (?!: nx-ny) of the cellulose awake film is preferably in the range of 〇~0.02. When the thickness is dnm, Rth/d is preferably in the range of 〇~0.04. In the present specification, the negative Re means that the transparent support in-plane retardation axis is in the TD direction, and the negative Rth means the thickness direction refraction. The rate is greater than the in-plane average refractive index. Examples of the polymer constituting the transparent support include cellulose esters (e.g., cellulose acetate, cellulose propionate, cellulose butyrate), and polyolefins (e.g., borneol polymerization) .), poly(meth) acrylate (eg polymethyl methacrylate), -54 - 1375093 polycarbonate, polyester and Grinding, ortho-ene based polymer, from the viewpoint of low birefringence, cellulose ester and ornidene are preferred, and commercially available raw borneol-based polymers can be used in the order of 11 11 01 [(] 8 ft (share) system), B £0^^£;> (, 2£0>^011 (made by 曰本ΖΕΟΝ), especially when using a protective film as a polarizing plate, cellulose ester Preferably, the lower fatty acid ester of cellulose is more preferred. The lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). It is also possible to use a cellulose acetate propionate or a cellulose acetate butyrate mixed fatty acid ester. Among the lower fatty acid esters of cellulose, cellulose acetate is preferred. The thiol substitution degree is preferably 2.50 to 3.00, more preferably 2 to 75 to 2.95, and particularly preferably 2.80 to 2, 90». The cellulose ester has a viscosity average polymerization degree (DP) of preferably 250 or more, more preferably 290 or more. Molecular weight average molecular weight, average molecular weight of Μη coefficient measured by gel permeation chromatography of cellulose ester The distribution is narrower. The Mm/Mn is preferably 1.0 to 5.0, more preferably 1.3 to 3.0, and particularly preferably 1.4 to 2.0.) In the cellulose ester, the second position of the cellulose is the third position and the first The hydroxyl group at the 6 position is not uniformly substituted, but the degree of substitution at the sixth position tends to be small. In the present invention, the degree of substitution of the sixth position of the cellulose ester is preferably the same as or higher than the second position and the third position. The ratio of the degree of substitution of the sixth position is preferably 30 to 40% with respect to the total of the degree of substitution of the second position, the third position, and the sixth position. The ratio of the degree of substitution at the sixth position is preferably 31% or more, particularly preferably 32% or more. The degree of substitution at the sixth position is preferably 0.88 or more. The 6th position of the cellulose may be substituted with a fluorenyl group having 3 or more carbon atoms (Example 3 - 55 - 1375093 such as a propyl fluorenyl group, a butyl fluorenyl group, a pentamidine group, a benzamidine group or an acryl fluorenyl group) in addition to the acetyl group. The degree of substitution at each position can be determined by NMR. For the cellulose ester having a high degree of substitution at the sixth position, the synthesis example 2 and the paragraph number 0051 to 0052 described in the synthesis example 1 and the paragraph number 0048 to 0049 described in paragraphs 0043 to 0044 of JP-A No. 11-5851 can be referred to. Synthesis Example 3 described above was synthesized. In order to improve mechanical properties or increase the drying speed, a plasticizer may be added to P* in the cellulose ester film. A phosphate or a carboxylate can be used as the plasticizer. Phosphate ester

I oxime includes triphenyl phosphate (TPP) and tricresyl phosphate (TCP). Carboxylic acid esters such as phthalic acid esters and citric acid esters are typical examples. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP). And diethylhexanoate (DEHP). Examples of the citrate include o-ethenyl triethyl citrate (0 ACTE) and o-butyl decyl citrate (OACTB). Examples of other carboxylic acid esters include butyl oleate, methyl acetyl linoleate, dibutyl phthalate, and various trimellitic acid esters. It is better to use the brewed vinegar to make it fit! 1 (DMP, DEP, DBP, DOP, DPP, DEHP). Especially good for DEP and DPP. The amount of the plasticizer added is preferably from 0.1 to 25% by mass, more preferably from 1 to 20% by mass, particularly preferably from 3 to 15% by mass based on the amount of the cellulose ester. Anti-deterioration agents (e.g., antioxidants, peroxide decomposers, radical inhibitors, metal inerting agents, acid scavengers, amines) may also be added to the cellulose ester film. The anti-deterioration agent is described in each of the publications of Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The amount of the anti-deterioration agent added is preferably 0. 0 1 to 1% by mass of the prepared solution (coating liquid), more preferably 〇 1 〇 1 to 〇 2% by mass. If the amount added is less than 〇 · 〇 1 (S) -56 - 1375093% by mass, the effect of the anti-deterioration agent is hardly observed. If the amount added is more than 1 mass%, there is a case where the anti-deterioration agent flows out (bleeds out) to the surface of the film. Examples of particularly preferred anti-deterioration agents are butylated hydroxytoluene (BHT) and triphenylmethylamine (TBA). Furthermore, in order to prevent light pipelining, a very small amount of dye may be added. From the viewpoint of the transmittance, it is preferable to adjust the kind and amount so that the transmittance of light having a wavelength of 420 nm becomes 50% or more. The amount of dye added is preferably o. oippm ~ 1 ppm 纤维素 in the cellulose ester film, in order to control Re hysteresis or Rth hysteresis, ® can add hysteresis 値 control agent. With respect to 100 parts by mass of the cellulose ester, the late stagnation controlling agent is preferably used in the range of 0.01 to 20 parts by mass, more preferably in the range of 0. 05 to 15 parts by mass. The best system is used in the range of 〇.1~1〇 parts by mass. It is also possible to use more than two types of hysteresis control agents. The hysteresis control agent is published in the publications of International Publication No. WO01/8 8 5 74, International Publication WOOO/2619, and the publications of JP-A-2000-1 1 1 9 1 4 and 2000-27 5 4 3 4 There are records. A cellulose ester film can be produced by a solvent casting method using a solution containing a cellulose ester and other components as a coating. The coating liquid is cast on a drum or a belt to evaporate the solvent to form a film. The coating liquid before casting is preferably adjusted to have a solid content of 18 to 35%. It is also possible to cast a coating liquid of two or more layers. The surface of the drum or belt is preferably mirrored. The method for casting and drying in the solvent casting method is disclosed in U.S. Patent No. 23 3 63 1 0, No. 23 67603, No. 2,492,078, No. 2,492,977, No. 2,492,978, No. 2,607,704, and No. 2,739,069. No. 2739070, British Patent No. 640731, and 736892, each specification, special public Zhao 45-45 54 'the same as 49-56 1 4 1375093, special opening 60-176834, the same 60-203430, the same 62- 1 It is described in each bulletin of 1 5 03 5 . The coating liquid is preferably cast on a drum or belt having a surface temperature of 10 ° C or less. Drying after casting for 2 seconds or more is preferred. Further, a method in which the obtained film is peeled off from a drum or a belt, and then dried in a high-temperature air which is gradually changed in temperature from 100 to 160 ° C to evaporate the residual solvent (described in Japanese Patent Publication No. 5-17844) . By this method, the time from the start of the casting to the stripping can be shortened. In order to carry out the method, it is necessary to gel the coating liquid in the surface temperature of the flow delay drum or the belt. In the case of casting a plurality of cellulose ester solutions, a plurality of castings □ provided in the interval of the traveling direction of the support may be respectively cast out of each solution containing the cellulose ester, and a film may be formed while laminating (Special publications are published in the Gazettes No. 6 1 - 1 5 841 4, Special Kaiping 1 - 1 224 1 9 and Special Kaiping 1 1 - 1 9 82 8 5). In addition, it is also possible to form a film by casting a fiber and a voxel ester solution through two casting openings (Japanese Patent Publication No. 60-27562, JP-A-61-94724, JP-A-61-947245, No. Kai Zhao 61-104813

No., No. 6 1 - 1 5 84 1 3 and Special Kaiping 6- 1 3 493 No. 3, in the bulletin I). A casting method of a cellulose ester film in which a high-viscosity cellulose ester solution is cast in a low-viscosity cellulose ester solution to simultaneously extrude the high-viscosity and low-viscosity cellulose ester solution may be used. Kai Chong 5 6- 1 626 1 (published in bulletin). The cellulose ester film can be further subjected to a stretching treatment to adjust the hysteresis. The draw ratio is preferably in the range of 3 to 100%. Preferably, the tenter is stretched. In order to control the slow phase axis with high precision, the difference between the gripping speed and the detachment time point of the left and right tenter is preferably as small as possible. The stretching treatment is described on page 37, line 8 to page 38, line 8, of the International Publication Wool/88574, 1375093 booklet. ' Surface treatment can be applied to the cellulose ester film. The surface treatment is, for example, a corona discharge treatment, a glow discharge treatment, a flame treatment, an acid treatment, an alkali treatment, and an ultraviolet irradiation treatment. From the viewpoint of maintaining the planarity of the film, it is preferable to make the temperature of the cellulose ester film below the Tg (glass transition temperature) in the surface treatment, specifically below 150 °C. When formed by film formation, the thickness of the cellulose ester film can be adjusted by lip flow rate and line speed, or by stretching or compression. Since the moisture permeability differs depending on the main raw material used for the ®, the protective film of the polarizing plate can be made to have a better moisture permeability by adjusting the thickness. Further, when it is produced by film formation, the free volume of the above cellulose ester film can be adjusted by drying temperature and time. In this case, since the moisture permeability is also different depending on the main raw material used, the protective film can be made to have a better moisture permeability by adjusting the free volume. The hydrophilicity of the cellulose ester film can be adjusted by additives. The addition of a hydrophilic additive to the free volume improves the moisture permeability, and conversely, the addition of a hydrophobic additive reduces the moisture permeability. By adjusting the moisture permeability of the cellulose® ester film by such various methods, the protective film of the polarizing plate can be protected from the polarizing plate by the polarizing plate in the range of better moisture permeability. The film can inexpensively produce a polarizing plate having optical compensation ability with high productivity. [Polarizing Plate] The polarizing plate used in the liquid crystal display device of the present invention is composed of a polarizing film and a pair of protective films that hold the polarizing film. The polarizing film is, for example, an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, or a polyolefin-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film can be generally produced by using a polyvinyl alcohol-based film -59-1375093. The type of the protective film is not particularly limited, and cellulose esters such as cellulose acetate, cellulose acetate butyrate, and cellulose propionate, polycarbonate, polyolefin, polystyrene, and polyester can be used. The transparent protective film is usually supplied in a roll form, and it is preferable that the long polarizing film is continuously bonded so that the longitudinal direction thereof is uniform. Here, the alignment axis (slow phase axis) of the protective film may be in either direction. Further, the angle between the slow axis (alignment axis) of the protective film and the absorption axis (tensile axis) of the polarizing film is not particularly limited, and can be appropriately set in accordance with the purpose of the polarizing plate.

The polarizing film and the protective film can be attached by a water-based adhesive. The adhesive solvent in the aqueous adhesive is dried by being diffused in the protective film. When the moisture permeability of the protective film is high, the higher the drying, the faster the drying, and the higher the productivity. However, if it is too high, the moisture enters the polarizing film under the use environment (high humidity) of the liquid crystal display device. Reduce the polarizing power. The moisture permeability of the optical compensation sheet is determined by the thickness, free volume, or hydrophilicity of the polymer film (and the polymerizable liquid crystal compound). The moisture permeability of the protective film of the polarizing plate is preferably in the range of 100 to 1 000 (g/m2) / 24 hours, more preferably in the range of 300 to 700 (g/m2) / 24 hours. In the present invention, for the purpose of thinning or the like, one of the protective films of the polarizing film may also serve as a support for the anisotropic layer, or may be an optically anisotropic layer itself. The optically anisotropic layer and the polarizing film are preferably fixed from the viewpoint of preventing the displacement of the optical axis or the intrusion of foreign matter such as dust. In the fixed laminate, for example, a suitable method such as a bonding method via a transparent adhesive layer can be employed. The type of the adhesive or the like is not particularly limited. However, from the viewpoint of preventing the change in optical characteristics of the member, etc., it is preferable to use a high-temperature program at the time of hardening or drying -60-1375093 at the time of the subsequent treatment. For those who do not need long-term hardening treatment or drying time. From these viewpoints, it is preferred to use a hydrophilic polymer binder or an adhesive layer.

It is also possible to use a protective film for various purposes such as water resistance based on the protective film on one or both surfaces of the polarizing film, and to prevent polarization of a suitable functional layer such as an antireflection layer or an antiglare layer by preventing surface reflection or the like. board. The antireflection layer can be suitably formed into a light interference film or the like which is, for example, a coating layer of a fluorine-based polymer or a multilayer metal deposition film. Further, the formation of the anti-glare treatment layer may be imparted to the surface fine uneven structure or the like by a resin coating layer containing fine particles, or an embossing process, a sanding process, or an etching process, for example, so that the surface reflected light energy can be appropriately Diffusion. Further, in the above micro' particles, for example, vermiculite having a mean particle diameter of 0.5 to 2 Ομϊη or calcium oxide, aluminum oxide or titanium oxide, cerium oxide or tin oxide, indium oxide or cadmium oxide, cerium oxide or the like can be used. Conductive inorganic fine particles or one or more selected from the group consisting of crosslinked or uncrosslinked organic fine particles composed of a suitable polymer such as polymethyl methacrylate or polyurethane. Further, the adhesive layer and the adhesive layer may contain the fine particles to exhibit light diffusibility.

In the present invention, the optical properties and durability (short-term, long-term storage) of the polarizing plate composed of the protective film, the polarizing film, and the transparent support are preferably compared with commercially available SUPERHI (for example, HLC2 manufactured by Sanritz Co., Ltd.). 5618, etc.) Performance equal to or greater. Specifically, the visible light transmittance is above 42.5 %, and the degree of polarization 々 ({(丁?一丁(〇/(丁?+1'〇}20.9995 (in which the parallel transmittance, Tc orthogonal transmittance) When placed at a temperature of 60 ° C, a humidity of 90% RH 1375093 for 500 hours, and at 80 ° C for about 500 hours in a dry environment, the rate of change of light transmittance before and after is based on absolute enthalpy. % or less, preferably 1% or less, and the rate of change of the degree of polarization is 1% or less, preferably 0.1% or less, based on the absolute enthalpy. The display mode of the liquid crystal display device which can be used in the present invention is not particularly limited, but is not particularly limited. Preferably, the liquid crystal display device usable in the present invention is not effective in the above display mode, and is also effective in the STN mode, the TN mode, and the OCB mode.

The following examples are given to more specifically illustrate the invention. The materials, reagents, masses, ratios, operations, and the like shown in the following examples can be appropriately changed as long as they are out of the scope of the present invention. Therefore, the scope of the invention is not limited to the specific examples below. (Production of Transparent Support S-1) A commercially available cellulose tetraacetate film FUjitec TD80UF (manufactured by Fuji Photo Film Co., Ltd., Re = 3 nm, Rth = 50 nm) was used as the transparent support S-1. (Production of Transparent Support S-2) The following composition was placed in a mixing tank, stirred while being heated, and each component was dissolved to prepare a cellulose acetate solution. -62 - 1375093

[Table 1] Cellulose acetate solution composition (%) Inner layer outer layer acetylation degree 60.9% cellulose acetate 20.89 19.78 triphenyl phosphate (plasticizer) 1.63 1.54 biphenyl diphenyl phosphate (plasticizer) 0.8 15 0.770 Dichloromethane (1st solvent) 61-22 62.12 Methanol (2nd solvent) 14.83 15.03 1-butanol (3rd solvent) 0.313 0.320 Vermiculite (972, manufactured by Japan Aerosil Co., Ltd.) 〇〇0.160 Hysteresis値Rising agent S-2-1 0.302 0.280 Using the three-layer co-casting die, the obtained coating liquid for the inner layer and the coating liquid for the outer layer were cast on a rotating cylinder cooled to 〇°c. The film having a residual solvent content of 7 〇 mass% was fixed by a needle tenter at both ends, and the draw ratio in the transport direction was 110%, and the transport was performed at 8 (TC dry, and when the residual solvent amount became 10%) It was dried at 110 ° C. Then, it was dried at a temperature of 14 Torr for 30 minutes to prepare a cellulose acetate film (outer layer: 1375093 3 μm, inner layer: 74 μm, outer layer: 3 μmη) of a residual solvent of 0.3% by mass. The optical properties of the film obtained from the transparent support S-2 为 are Re = 8 nm ' Rth = 82 nm » (Production of transparent support s-3) The following composition was placed in a mixing tank, and stirred while heating to dissolve each component to prepare a cellulose-deposited solution. "Knowledge Technology No. 157" (published in Aztec Co., Ltd., 2003) [Table 2]

Composition of deuterated cellulose solution (%) Deuterated cellulose (acetate group 1.2, degree of substitution of diammonium 1.3) 24.0 Mixed solvent (table) 75.0 Hysteresis 値 rising agent S-3-1 0-70 2-(2 ,-hydroxy-5'-methylphenyl)benzotriazole 0.70 2-(2,-hydroxy-3',5,-di-t-butylphenyl)-5-chlorobenzotriazolium.〇 5 2-(2,-Hydroxy-3',5'-di-t-butylphenyl)benzotriazolium·〇2 vermiculite particles (methanol vermiculite sol, manufactured by Nissan Chemical Industries Co., Ltd.) 006 Lemon Ethyl acetate (monoester and diester mixed in 1:1) _005 【化29】

Ch3 (S — 3 — 1) (§) -64 - 1375093 [Table 3] Mixed solvent composition (%) Methyl acetate 80.0 Acetone 5.0 Methanol 7.0 Ethanol 5.0 Butanol 3.0

Then, it was filtered by a filter paper (manufactured by Toyo Filter Co., Ltd., #63) having an absolute filtration precision of 〇1 mm, and filtered by a paper (FH025, manufactured by Poul Co., Ltd.) having an absolute accuracy of 2.5 μm. The above coating liquid was warmed to 35 ° C, and passed through a die to a mirror stainless steel drum set to a diameter of 3 m set at -1 5 °C. The die used is a shape similar to that described in the Japanese Patent Publication No. 3 M2 3 No. 3. Further, the casting speed was 1.00 m/min, and the casting width was 250 cm. After the residual solvent was peeled off at 200% by mass, it was taken up at 13 (TC dry, when the residual solvent became 1% by mass or less) to prepare a bismuth cellulose film. The obtained film was trimmed at both ends by 3 cm. The portion of 2 to 10 mm is given a knurling height of 1 〇〇μηι, and is taken up into a roll of 3000 m. The film is used as a transparent support s-3 by the biaxial stretching (Re=l〇nm (Rth=40 nm). (Preparation of the coating liquid for the alignment layer a-1) The following composition was prepared and filtered through a polypropylene filter having a pore size of 30 μm, and used as a coating liquid for the alignment layer AL-1. 1375093. [Table 4] Composition of coating liquid for alignment layer (%) Modified polyvinyl alcohol AL-1-1 4.0 1 Water 72.89 Methanol 22.83 Glutaraldehyde (crosslinking agent) 0.20 Citric acid 0.008 Bisphenol monoester 0.029 Lemon Diethyl acetate 0.027 Triethyl citrate 0.006 [Chemical 3 0] -ch2-ch- -ch2-ch- -ch2-ch-

OCOCH3 OCONHCH2CH2〇CH2〇C=CH2 x/y/z = 86.3/12.0/1.7 CH3 (AL-1 - 1) (Preparation of coating liquid AL-2 for alignment layer) The following composition was prepared by the aperture 30. A filter made of polypropylene of μιτι was used for filtration, and it was used as a coating liquid AL-2 for an alignment layer. -66 - 1375093 [Table 5]

Composition of coating liquid for alignment layer (%) Polyvinyl alcohol PVA-2 03 (manufactured by Kuraray) 4.0 1 Water 72.89 Methanol 22.83 Glutaraldehyde (crosslinking agent) 0.20 Citric acid 0.008 Bain citrate 0.029 Diethyl citrate 0.027 Triethyl citrate 0.006

(Preparation of the coating liquid LC-1 for the optically oriented layer) After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm, and used as a coating liquid for an optical anisotropic layer. -1. [Table 6] Composition of coating liquid for optical anisotropic layer (%) Iff% C3 r τ /">· 4 4 n 悴λΛ 33 u - i · ijr /r η υ . υ / rod-shaped liquid crystal (LC-1-2) 2.60 to palm (LC-1-3) 2 1.07 to palm (LC-1-4) 1.67 chain transfer agent (LC-1-5) 0.67 photopolymerization initiator (LC -1-6) 0.67 methyl ethyl ketone 66.65 -67 - 1375093. 31] CH2=( ch3 )H^C〇〇hQ^〇C〇-^-« -ch=ch2 fT Π — 1 — 1 ^

LC-1-1: Synthesized according to the method described in Angew. Makromol. Chem., pp. 183, p. 45 (1990). LC-1 -2 : Synthesized by condensing 4-(6-propenyloxyhexyloxy)benzoic acid synthesized by the method described in EP 1174411 B1 with 4·propylcyclohexylphenol (manufactured by Kanto Chemical Co., Ltd.) . -68- 1375093. LC-1 -3 : 4-(6-propenyloxyhexyloxy)benzoic acid synthesized by the method described in [?117 44 1181 and from WO/2 001 04 0154A1 The 4-hydroxy-4'-(2-methylbutyl)biphenyl synthesized by the method described in the above method was synthesized by condensation. LC-1 -4 : synthesized by the method described in EP 138919 9A1" LC-1-5:

After methacrylate hydroxypropyl ester (manufactured by Andrich) was methylsulfonated, it was reacted with 4-propylcyclohexylphenol (manufactured by Kanto Chemical Co., Ltd.), followed by addition of hydrogen sulfide to synthesize LC-1-6: 4-propyl group After cyclohexyl hydrazine (manufactured by Kanto Chemical Co., Ltd.) is trifluoromethanesulfonic acid, it is converted into a biphenyl group by a Suzuki coupling reaction by phenyl phorulonic acid. Further, after the 4' position of the phenyl group is oxime by isobutyric acid chloride and aluminum chloride, the carbon at the α position of the carbonyl group is brominated by bromine, and then synthesized as a hydroxyl group by a base. φ (Preparation of the coating liquid LC-2 for optical anisotropic layer) After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm to make it an optical heterogeneous layer.闬 Coating liquid LX-2. [Table 7] Composition of coating liquid for optical anisotropic layer (%) Disc liquid crystal (LC-2-1) 19.2 Additive (LC-2-2) 0.2 Photopolymerization initiator (LC-2-3) 0.6 Methyl group Ethyl ketone 80.0 (§) -69- 1375093,

Synthesizing OR by the method described in JP-A-2001-Γ66 1 47

OR OR R=Ci2H25 according to Tetrahedron Lett., vol. 43, pp. 6793 (2002)

The method described is synthesized.

The compound described in Japanese Laid-Open Patent Publication No. Hei 03- 1 29 3 52. (Preparation of the coating liquid LC·3 for the optically oriented layer) After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 〇·2 μm, and used as a coating liquid for an optical anisotropic layer. LC-3» • 70 - 1375093. [Table 8] Composition of coating solution for optical anisotropic layer (%) Rod liquid crystal (LC-3-1) 15.2 Rod liquid crystal (LC-3-2) 4.2 Additive (LC -3-3) 0.2 Photopolymerization Initiator (LC-3-4) 0.6 Methyl ethyl ketone 80.0 , [Chemical 3 3] . CH3 CH2=CHC00-(CH2)6-0-^~^-C〇0 -^~^-0C0-^~~^-0(CH2)60C0-CH=CH2 (LC _ 3 — 1)

(L C — 3 — 2)

The synthesis was carried out according to Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. A, 260 巻, 51 pages (1 995). 8 -71- 1375093

(Preparation of the coating liquid LC-4 for the optically oriented layer) After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 2 μm, and used as an optical anisotropic layer coating. Liquid LC-4. [Table 9] Composition of coating solution for optical anisotropic layer (%) Rod liquid crystal (LC-1-1) 6.67 Rod liquid crystal (LC-1-2) 2.60 Pair of palm (LC-1-3) 2 1.07 For palm powder (LC-1-4) 1.67 Chain transfer agent (LC-1 -5) 0.67 Photopolymerization initiator (LC-Bu 6) 0.67 Leveling agent (S-22) 0.20 Methyl ketone 66.45 3 -72 - 1375093. [Chemical 3 4] CHa CH2=CHCOO-(CH2)r servant. . Hey. Points 0(CH2)60C0-CH=CH2 (LC-1 - 1)

LC-1-1, LC-1-2, LC-1 -3 'LC-1 -4 'LC-1-5 and LC-1 -6 were synthesized in the same manner as above. (Preparation of the coating liquid LC-5 for the optically oriented layer) The following composition was prepared and filtered by a polypropylene filter having a pore size of 22 μm, and used as a coating liquid for an optical anisotropic layer. -5 1375093. [Table 10]._ Composition of coating liquid for optical anisotropic layer (%) Disc liquid crystal (LC-2-1) 19.2 Photopolymerization initiator (LC-2-3) 0-6 Horizontal alignment agent (S-22) 0-2 methyl ethyl ketone 79-8

[化3 5]

(LC-2 - 1) This was synthesized by the method described in JP-A-200-166147.

(LC-2-3) The compound described in JP-A-03-129352. (Preparation of the coating liquid LC-6 for the optically oriented layer) The following composition was prepared and filtered by a polypropylene filter having a pore size of 0.2 μm, and used as a coating liquid for an optical anisotropic layer LC- 6. 8 -74 - 1375093. [Table 1 1] Composition of coating solution for optical anisotropic layer (%) Rod liquid crystal (LC-3-1) 15.2 Rod liquid crystal (LC-3-2) 4.2 Photopolymerization initiator ( LC-3-3) 0.6 Leveling agent (S-22) 0.2 Methyl ethyl ketone 80.0

[Chem. 3 6]

CH2:=CHC00-(CH2)6-0

o(ch2)6oco-ch=ch2 (L C— 3 — 1)

Synthesized according to Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. A, pp. 26, 51 (1995).

(Preparation of the coating liquid LC-7 for the optically oriented layer) After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm, and used as a coating liquid for an optical anisotropic layer. -7. 1375093.

[Table 12] Composition of coating solution for optical anisotropic layer (%) Rod liquid crystal (LC-1-1) 6.67 Rod liquid crystal (LC-1-2) 2.60 Pair of palm (LC-1-3) 2 1.07 For palm (LC-1-4) 1.67 chain transfer agent (LC-1-5). 0.67 photopolymerization initiator (LC-1-6) 0.67 methyl ethyl ketone 66.65 [chemical 3 7] CH3 Ο rτ r . — 1 - τ'»

CH2=CHC00-(CH2)6-0 〇 coo (LC- 1-2)

C3h7 CH2=CHCOO-(CH2)r

Ch3 ch2—ch*-c2h5 (LC-1 - 3) 1375093

HS(CH2)2COO —(CH2)3—ο

(LC - 1 - 5) (LC-1 - 6) * (Preparation of coating liquid LC-8 for optically oriented layer) After preparing the following composition, a polypropylene filter having a pore size of 0.2 μη! To filter, use the palm of the coating liquid LC-8 for the optically oriented layer. [Table 13] Composition of coating liquid for optical anisotropic layer (%) Disc liquid crystal (LC-2-1) 19.2 Additive (LC-2-2) 0.2 Photopolymerization initiator (LC-2-3) 0.6 Methyl group Ethyl ketone 80.0 [Chemical 3 8]

1375093. tr

$

OR

R=C 12^25 Page 43 page 6793 (2002) Synthesize according to the method described by Tetrahedron Lett.

(Preparation of the coating liquid LC-9 for optically oriented layer) After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 2 μm, and used as an optical anisotropic layer coating. Liquid LC-9 » 【Form】 Composition of optically isotropic layer coating solution (%) Rod liquid crystal (LC-3-1) 15.2 Rod liquid crystal (LC-3-2) 4.2 Additive (LC-3-4 0.2 Photopolymerization initiator (LC-3-3) 0.6 Methyl ethyl ketone 80.0 8 -78 - 1375093. 39 ch3 j=CHCOO-(CH2)6-〇 servant. heart. c. Servant (LC—3 — 1) h3c

Coo

COO(CH2)4OC〇-CH=CH2 CH2=CHCO〇-(CH2)4-〇 (L C — 3 — 2)

CCI3

(L C - 3 - 3), N - CCI3 (one side gelation of cellulose ester film)

The cellulose ester film was passed through a dielectric heating roll at a temperature of 60 ° C, and the surface temperature of the film was raised to 40 ° C, and then an alkali solution of the composition shown below was applied at 4 ml/m 2 using a bar coater. Then, after standing for 10 seconds under a steam type far infrared heater (manufactured by Noritake Co., Ltd.) heated to 1 1, pure water was applied at 3 m Ι/m 2 using the same rod coater. The film temperature at this time is 40 ° C (§) -79 - 1375093. Next, water was washed by a spray coater and water was removed by an air knife, and after repeated three times, it was left to stand in a drying zone at 70 ° C for 2 seconds to be dried. [Table 15] Composition of alkali solution (%) Potassium hydroxide 4.7 Water 14.7 Isopropanol, 64.8 Propylene glycol 14.8 Surfactant (SF-1) 1.0 [Chem. 40]

Ci 6H33〇(CH2CH2〇)i 〇H ( S F — 1 )

[Example 1-1] After the saponification treatment was performed on one surface of the transparent support S1 by the one-side saponification treatment, the coating liquid for coating for the alignment layer AL-1 was applied thereon by a wire bar coater of #14. It was dried in a warm air of °C for 60 seconds and then in a warm air of 90 ° C for 150 seconds to form an alignment layer having a thickness of 1. Ομηι. Next, the formed alignment layer was subjected to a rubbing treatment with respect to the retardation axis direction of the transparent support, and then the coating liquid LC-1 for an optical anisotropic layer was applied thereon by a wire bar coater of #3. The mixture was cooked by heating at 60 ° C for 1 minute to form an optically anisotropic layer having a uniform liquid crystal phase. Furthermore, immediately after the ripening, the optically anisotropic layer is used in an environment having an oxygen concentration of 3% or less. 〇1^1;1'/_1' was produced by irradiating polarized light UV (illuminance: 200 mW/cm2, irradiation amount: 200 mJ/cm2) with the transmission axis of the polarizing plate being the direction of the slow axis of the transparent support. 1 optical compensation sheet. After the optically anisotropic layer is fixed, even if the temperature is raised, it is not 3 - 80 - 1375093. The liquid crystal phase is displayed. The thickness of the optically oriented layer is 1·3 μm. The following evaluation was performed about the obtained optical compensation sheet. Adhesion test (dry adhesion) The presence or absence of peeling was visually observed by the cross cutting method, and the following three-stage evaluation was performed.

〇: Almost no peeling was observed △: 10% or more of peeling was observed X: 50% peeling was observed (wet close) A 24x36 mm sample was immersed in hot water of 60 ° C for 5 minutes, and visually observed for peeling or not. The following three-level evaluation was performed. 〇: Almost no peeling was observed. △: 10% or more of peeling was observed. X: 50% peeling was observed (phase difference measurement). With KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.), the positive retardation at 589 nm値Re and the slow phase axis are used as the rotary axis, and the hysteresis (Re(40) and Re(-40) when the sample is tilted by ±4 〇 is measured. [Example 1-2] The coating liquid LC-1 for an optical anisotropic layer in Example 1-1 was changed to the coating liquid LC-2 for an optically anisotropic layer, and the rest was the same as in Example 1-1. Perform 'to make an optical compensation sheet. [Example 1 - 3 ] -81 - 1375093. The coating liquid LC·1 for the optically anisotropic layer in Example 1-1 was changed to the coating liquid LC-3 for the optical anisotropic layer, and the rest was carried out. Example 1-1 was carried out in the same manner to prepare an optical compensation sheet. [Example 1-4] The transparent support S-1 in Example 1-1 was changed to the transparent support S-2, and the rest was carried out in the same manner as in Example 1-1 to prepare an optical compensation sheet. [Example 1-5] * The transparent support S-ι in Example 1-1 was changed to a transparent support S-3. The rest was carried out in the same manner as in Example 1-1 to prepare an optical compensation sheet. [Comparative Example 1] The coating liquid AL-1 for the alignment layer in Example 1-1 was changed to the coating liquid AL-2 for the alignment layer, and the same procedure as in Example 1-1 was carried out to prepare an optical compensation sheet. The results of the adhesion evaluation of Examples 1 -1 to 5 and Comparative Example 1-1 are shown in Table 1-1, and the optically different directions of Examples 1-1 to 1-3 and 1-5 and Comparative Example 1-1. The phase difference measurement results of the layers are shown in Table 1-2. Table 1-1 • [Table 16]

Sample dry m Example 1-1 Example 1 - 2 Example 1 - 3 Example 1-4 Example 1 - 5 〇〇 Comparative Example 1 - 1 XX 8 - 82 - 1375093. [Table 17] Table 1-2 Sample Re Re (40) Re (-4 〇) Example 1 - 1 9.8 60.2 59.8 Example 1-2 15.8 6 1.2 60.0 Example 1-3 4.7 5 1.6 50.7 Example 1 4 6.6 53.8 57.4 Example 1-5 6.9 55.2 56.9 Comparative Example 1 - 1 9.9 59.6 61.9

Further, with respect to the optical compensation films of Example 1-1 and Examples 1-3 to 1-5, the cross-sectional sections were observed by a transmission electron microscope, and it was confirmed that the rod-shaped molecules were aligned at less than 3 degrees with respect to the transparent substrate. With respect to the optical compensation film of Example 丨_2, the cross-sectional section was observed by an optical microscope, and it was confirmed that the discotic molecules were aligned at less than 3 degrees with respect to the transparent substrate. [Example 1_6] (Production of polarizing plate with optical compensation sheet) The laminate of the optical compensation sheet and the optically anisotropic layer of Examples 1-1 to 1-5 of the present invention and Comparative Example 1-1 and the city A Fujitec TD80UF (manufactured by Fuji Photo Film Co., Ltd., Re = 3 nm, Rth = 50 nm) sold was immersed in a 1.5 mol/L sodium hydroxide aqueous solution at 55 ° C for 2 minutes. Subsequently, it was washed in a water bath at room temperature to neutralize at 30 ° C using 〇 5 mol / L of sulfuric acid. It was again washed in a water bath at room temperature and dried in a warm air at 100 °C. Then, water washing and neutralization treatment were carried out 'two saponified films were used as a protective film for the polarizing plate - 83 - 1375093. 'With a polyvinyl alcohol-based adhesive, the two sides of the polarizing film were adhered by a roll-to-roller. To make an integrated polarizer. The first aspect of the present invention is excellent in productivity and the optically anisotropic layer exhibits a good planar shape. In the comparative example, not only the adhesion is insufficient, but also the one-side saponification treatment before the application of the alignment layer causes a decrease in productivity, and a problem such as a saponification bath when polluting the polarizing plate is caused.

[Examples 1-7J

(Production of VA-LCD liquid crystal display device) The lower polarizing plate of a commercially available VA-LCD (SyncMaster 173P, manufactured by Samsung Electronics Co., Ltd.) was peeled off, and a general polarizing plate was bonded to the upper side by an adhesive, and the lower side was bonded to the lower side. A polarizing plate with optical compensation sheets of Embodiments 1-1 and 1-2 of the first aspect of the present invention, which are produced in Embodiments 1 to 6 of the first aspect of the invention, to optically The liquid crystal display device of the present invention was produced by forming a directional layer on the glass surface of the liquid crystal cell substrate. The cross-sectional view of the liquid crystal display device produced and the angular relationship of the optical axes of the respective layers are shown in Fig. 5. In Fig. 5, a 41-type polarizing layer, a 42-series transparent support, a 43-series alignment layer, a 44-series optically anisotropic layer (an optical compensation sheet of the first aspect of the present invention of 41 to 44), and a 45-type polarizing plate. The protective film, the 46-series liquid crystal cell glass substrate, the 47-series liquid crystal cell, and the 48-type adhesive layer. Further, the arrow in the polarizing layer 41 indicates the direction of the absorption axis, and the arrow in the optically anisotropic layer 44 or its support 44 and the protective film 45 indicates the direction of the slow axis, and the circle indicates the method of the arrow relative to the paper surface. Line direction (Evaluation of VA-LCD liquid crystal display device) The viewing angle characteristics of the produced liquid crystal display device were measured by a viewing angle measuring device (EZ Contrast 160D, manufactured by ELDIM Co., Ltd.) -84 - 1375093. Further, it was evaluated by visual observation particularly in the direction of inclination of 45 degrees. The comparative characteristics measured by EZ Contrast of Examples 1-7 are shown in Fig. 6, and the visual evaluation results are shown in Table 1-3. [Table 18] Table 1-3 Example of visual evaluation results of the sample 1-7 White display and 黒 display are all less color deviation, and the tone characteristics of the middle tone are good.

[Example 2-1] After the saponification treatment was performed on one surface of the transparent support S-1 by the above-described one-side saponification treatment, the coating liquid for coating for the alignment layer AL-1 was applied thereon by a wire bar coater of #14. It was dried in a warm air of 60 ° C for 60 seconds and then in a warm air of 90 ° C for 150 seconds to form an alignment layer having a thickness of 1. μm. Next, the formed alignment layer was subjected to a rubbing treatment with respect to the retardation axis direction of the transparent support, and then the optical anisotropic layer coating liquid LC-4 was applied thereon by a #3 wire coater. The mixture was cooked by heating at 60 ° C for 1 minute to form an optically anisotropic layer having a uniform liquid crystal phase. Furthermore, immediately after the ripening, the optically anisotropic layer is used in an environment having an oxygen concentration of 3% or less. 〇1^1^-1' was produced by irradiating polarized light UV (illuminance 200 mW/cm 2 , irradiation amount 200 mJ/cm 2 ) so that the transmission axis of the polarizing plate became the retardation axis direction of the transparent support. Optical compensation sheet. After the optically anisotropic layer is immobilized, the liquid crystal phase is not displayed even if the temperature is raised. The thickness of the optically anisotropic layer is i.hm. -85 - 1375093. The following evaluation was performed about the obtained optical compensation sheet. (Panel evaluation) The optical compensation film produced in Example 2-1 was placed between a pair of polarizing plates arranged in a crossed Nicols, and illuminated from below, and the surface was visually evaluated. Evaluation criteria: ◎: There were almost no markings or defects in the test article. 〇: The part where the markings and defects occurred was observed in the test article. X: Most of the markings and defects were observed in the test article.

The X system is not suitable for the degree of manufacture. Further, the haze of the obtained optical compensation film was measured by using a haze meter "NDH2000", manufactured by Nippon Denshoku Industries Co., Ltd., according to IS K7 1 3 6:2000. The results of the planar evaluation and the measurement of the haze are shown in Table 1. (Phase Difference Measurement) The KOBRA 21 ADH (manufactured by Oji Scientific Instruments Co., Ltd.) uses the front retardation 値Re at 5 89 nm and the slow phase axis as the rotary axis to measure the hysteresis 値Re when the sample is tilted by ±40 degrees. 40), Re (-4〇p [Example 2-2] In addition to the coating liquid LC_4 for the optically anisotropic layer in Example 2-1, the coating liquid LC-5 for optical anisotropic layer was used. An optical compensation sheet was produced in the same manner as in Example 2-1. [Example 2_3] The coating liquid LC-4 for optical anisotropic layer in Example 2-1 was replaced with an optically isotropic layer coating layer. The optical compensation sheet was produced in the same manner as in Example 2-1 except for the liquid LC-6. (§) -86- 1375093.

[Comparative Example 2-1] - Example 2-1 was prepared except that the coating liquid LC-4 for an optical anisotropic layer was replaced with the coating liquid LC-7 for an optical anisotropic layer. 'The same was done to make an optical compensation sheet. - [Comparative Example 2-2] Example 2-1 was carried out except that the coating liquid LC-4 for an optical anisotropic layer in Example 2-1 was replaced with the coating liquid LC-8 for an optically anisotropic layer. * The same is done to make an optical compensation sheet. # [Comparative Example 2-3] Except that the coating liquid LC-4 for optical anisotropic layer in Example 2-1 was replaced with the coating liquid LC-9 for optical anisotropic layer, and Example 2-1 The same was carried out to produce an optical compensation sheet. In the same manner as in Example 2-1, the evaluation of the planar shape and the measurement of the phase difference of the optically anisotropic layer were carried out in the same manner as in Example 2-1 and Comparative Examples 2-1 to 2-3. The results of the planar evaluation are shown in Table 2-1, and the results of the phase difference measurement are shown in Table 2-2. • [Table 19] Table 2-1 Sample Surface Haze Example 2-1 ◎ 0. 37 Example 2-2 ◎ 0. , 4 1 Example 2-3 ◎ 0. , 39 Comparative Example 2-1 〇 0, .57 Comparative Example 2-2 〇0. .54 Comparative Example 2-3 〇0, .55 -87 - 1375093. [Table 20] Table 2-2 Sample Re Re(40) Re(-4〇) Implementation Example 2-1 11.5 60.7 60.5 Example 2-2 17.2 61.4 61.0 Example 2-3 5.7 50.6 50.3 Comparative Example 2 -1 9.8 60.2 59.8 Comparative Example 2-2 15.8 6 1.2 60.0 Comparative Example 2 - 3 4.7 5 1.6 50.7

Further, in the same manner as in Examples 2-1 to 2-3, except that the horizontal alignment agent S-22 was replaced with S-40 or S-56, an optical compensation film was produced. As a result, it was confirmed that the same surface was confirmed. Shape improvement effect. Further, with respect to the optical compensation films of Example 2-1 and Example 2-3, the cross-sectional sections were observed by a transmission electron microscope, and it was confirmed that the rod-shaped molecules were aligned at less than 3 degrees with respect to the transparent substrate. Further, with respect to the optical compensation film of Example 2-2, the cross-sectional section was observed by an optical microscope, and it was confirmed that the discotic molecules were aligned at less than 3 degrees with respect to the transparent substrate. [Example 2-4] (Production of polarizing plate with optical compensation sheet) The optical compensation sheets of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 of the present invention were separately commercially available. The Fujite CTD80UF (Fu = photographic film (R = 3 nm, R th = 50 nm) was immersed in 55. (:, 1.5 mol/L sodium hydroxide aqueous solution for 2 minutes. Then, it was washed in a water bath at room temperature, and at 3 〇β (: -88-1375093, the comparative characteristic measured was shown in the seventh In the figure, the visual evaluation results are shown in Table 2-3. [Table 21] Table 2-3 Visual evaluation results of the sample Example 2-5 The white display and the 黒 display are both small in color deviation and good in tone characteristics of the intermediate tone. .

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of an optical compensation sheet according to a first aspect of the present invention. Fig. 2 is a schematic cross-sectional view showing an example of an optical compensation sheet according to a second aspect of the present invention. Fig. 3 is a schematic cross-sectional view showing an example of a polarizing plate of the present invention. Fig. 4 is a schematic cross-sectional view showing an example of a liquid crystal display device of the present invention. Fig. 5 is a schematic cross-sectional view showing the layer structure of the liquid crystal display device produced in Examples 1-7 and 2-5 and the direction of the optical axis in the layer. Fig. 6 is a view showing the comparative characteristics of the liquid crystal display devices produced in Examples 1 to 7. Fig. 7 is a view showing the comparative characteristics of the liquid crystal display device produced in Example 2-5. [Description of component symbols] 11 Transparent support 1 2, 1 2 ' Optical anisotropic layer composed of liquid crystal compound - 90 - 1375093. 13, 13' Polymer layer 2 1 Polarization layer 22, 23 Protective film 24 λ/4 Functional layer of plate, anti-reflection film, etc. 3 1 Cold cathode tube 32 Reflective sheet

, 36 37 Light guide plate Dimming film for brightness enhancement film, diffusion film, etc. Liquid crystal cell Lower polarizing plate Upper polarizing plate 41 Polarizing layer 42 Transparent support 43 44

46 4 7 Alignment layer Optical anisotropic layer Polarizing plate protective film Liquid crystal cell glass substrate Liquid crystal cell 48 Adhesive 51 One-axis stretching optical compensation sheet

Claims (1)

Amendment to the Patent No. 094 1443 86 "Optical Compensation Sheet, Its Method of Making, Polarizing Plate" (Amended, June 26, 2012) X. Patent Application Range: 1. An optical compensation sheet comprising a transparent support, The transparent support is coated with a solution composed of a solvent containing 20% or more of water and dried to form a polymer layer formed on the surface of the polymer layer, and a liquid crystal composition containing at least one liquid crystal compound on the surface of the polymer layer. The optical anisotropic layer: wherein the front side retardation Re(Re) of the optical anisotropic layer is non-zero, and the normal direction of the optical compensation sheet which is the tilt axis (rotation axis) of the late phase axis in the plane, The hysteresis 测定 measured when the light of the wavelength ληιη is incident in a direction inclined by +40°, and the normal direction of the optical compensation sheet which is the tilt axis (rotation axis) with the in-plane slow axis is - the hysteresis 测定 measured when the light of the incident wavelength ληιη is inclined at 40° is substantially equal, and the polymer layer is chemically bonded to the optical anisotropic layer: wherein the polymer layer contains a reaction in the side chain Sex base The polymer. 2. An optical compensation sheet comprising a transparent support, a polymer layer on the support, and a liquid crystal composition comprising at least one liquid crystal compound and at least one fluorine-containing horizontal alignment agent on the surface of the polymer layer The optical anisotropic layer formed; wherein the front side retardation Re(Re) of the optical anisotropic layer is non-〇, with respect to a normal direction of a layer plane which is an oblique axis (rotation axis) of the late phase axis in the plane , the hysteresis 测定 measured when the light of the wavelength ληιη is incident in a direction inclined by +40°, and the normal direction from the plane of the layer which is the tilt axis (rotation axis) with respect to the in-plane slow axis The hysteresis 测定 measured when the light of the incident wavelength ληιη is incident in the oblique direction is substantially equal; wherein the height is 1375093. The modified molecular layer contains a polymer having a reactive group in the side chain. 3. The optical compensation sheet of claim 2, wherein the fluorine-containing horizontal alignment agent is a discotic compound. 4. The optical compensation sheet according to claim 2, wherein the fluorine-containing leveling agent is a compound represented by any one of the following formulas (I) to (III); In the formula, R1, ! ^2 and R3 each independently represent a hydrogen atom or a substituent, at least one substituent representing a fluorine atom, and χι, Χ2 and χ3 represent a single bond or a divalent linking group; Wherein R21, R22, r23, r24 and r25 each independently represent a hydrogen atom or a substituent; at least one substituent representing a fluorine atom; Formula (III) 1375093. Amendment r32o OR31 3 5 3 6 or a substituent - at least one substituent representing a fluorine atom 5. The optical compensation sheet according to claim 1 or 2, wherein the liquid crystal compound is a polymerizable discotic liquid crystal compound, and the optical anisotropic layer is a reactivity in the polymerizable discotic liquid crystal compound. A layer formed by a polymerization reaction. 6. The optical compensation sheet according to claim 1 or 2, wherein the liquid crystal compound is a discotic liquid crystal compound, and the optically anisotropic layer is formed by irradiating polarized light after horizontally aligning the discotic liquid crystal compound. Layer. 7. The optical compensation sheet of claim 1 or 2, wherein the liquid crystal compound is a discotic liquid crystal compound having a triphenylene skeleton. 8. The optical compensation sheet according to claim 1 or 2, wherein the liquid crystal compound is a polymerizable rod-like liquid crystal compound, and the optical anisotropic layer is polymerized by a reactive group of the polymerizable rod-like liquid crystal compound. And the layer formed. 9. The optical compensation sheet according to claim 1 or 2, wherein the liquid crystal compound is a rod-like liquid crystal compound, and the optically anisotropic layer is formed by aligning the rod-shaped liquid crystal compound with a cholesteric type and irradiating a polarized light. Layer. 10. The optical compensation sheet of claim 1 wherein the side chain has 1375093. The reactive group of the polymer which corrects the reactive group is a reactive group containing an ethyl group. 11. The optical compensation sheet according to claim 1 or 2, wherein the polymer layer contains a reactive group in a side chain and is selected from a polyvinyl alcohol derivative, a poly(meth) acrylate derivative. Or a polymer of polysaccharides. The optical compensation sheet of claim 1 or 2, wherein the transparent support system is a support which is at least one side alkali-saponified. 13. The optical compensation sheet of claim 2 or 2, wherein the transparent support comprises a cellulose derivative or a cyclic olefin derivative. Φ 14. The optical compensation sheet according to claim 1 or 2, which is used for a liquid crystal display device. 1 5 The optical compensation sheet of claim 14 wherein the display mode of the liquid crystal display device is a vertical alignment mode. 16. A method of producing an optical compensation sheet according to claim 1, which is carried out in the following sequential steps: coating a solution of a solvent composition containing 20% or more of water on a transparent support and allowing drying a step of forming a polymer layer; coating a liquid crystal composition containing at least one discotic liquid crystal compound having a reactive group on the surface of the polymer layer, and tilting molecules of the discotic liquid crystal compound at an average of less than 5° a step of aligning the horn; and a step of irradiating the polarized light to polymerize molecules of the liquid crystal compound to form an optically anisotropic layer; wherein the polymer layer contains a polymer having a reactive group in a side chain. 17. A method of manufacturing an optical compensation sheet according to claim 1, wherein the method comprises the steps of: coating a solution of a solvent having a water content of 20% or more on a transparent support and drying the solution Forming a polymer layer, step -4- 1375093. Correcting the step; coating a rod-like liquid crystal compound containing at least one reactive group and at least one liquid crystal composition of the palm powder on the surface of the polymer layer, the rod a liquid crystal compound molecule having a cholesteric alignment step at an average tilt angle of less than 5 °; and a step of irradiating polarized light to polymerize molecules of the liquid crystal compound to form an optically anisotropic layer; wherein the polymer layer is contained on the side A polymer having a reactive group in the chain. 18. The method of claim 16 or 17, wherein the solution comprising 20% or more of the solvent composition is based on polymerizing the molecules of the liquid crystal compound, and at least a part of the polymer is Reacting with at least a portion of the molecules of the liquid crystalline compound to form a chemical bond. A method of producing an optical compensation sheet according to claim 2, which is carried out in the following sequential steps: coating on the surface of the polymer layer formed on the transparent support contains at least one polymerizable group a liquid crystal composition of the discotic liquid crystal compound and at least one fluorine-containing horizontal alignment agent; a step of orienting the molecules of the discotic liquid crystal compound at an average tilt angle of less than 5°; and irradiating the polarized light to make the dish The step of polymerizing molecules of the liquid crystal compound to form an optically anisotropic layer; wherein the polymer layer contains a polymer having a reactive group in a side chain. A method for producing an optical compensation sheet according to claim 2, which is carried out in the following sequential steps: coating on the surface of the polymer layer formed on the transparent support, the coating contains at least one type of polymerization a liquid crystal composition of a rod-like liquid crystal compound and at least one fluorine-containing horizontal alignment agent: a step of aligning the molecules of the rod-like liquid crystal compound with an average tilt angle of less than 5 ° for cholesteric alignment; and irradiating the polarized light to The rod-like liquid crystal compound is divided into 1347093. The step of polymerizing to form an optically anisotropic layer: wherein the polymer layer contains a polymer having a reactive group in a side chain. 21. A polarizing plate having A polarizing element and at least one optical compensation sheet according to any one of claims 1 to 14. 22_ A polarizing plate as claimed in claim 21, which is used for a liquid crystal display device. 23. The polarizing plate of claim 22, wherein the display mode of the liquid crystal display device is a vertical alignment mode.