TW201200899A - Optical element and viewing angle improving method for polarizing film using said optical element - Google Patents

Abstract

This invention relates to an optical element constituted by an optically amisotropic layer, wherein the optically anisotropic layer contains organic pigments and has a three-dimentional refractive index satisfying the folloving relationship: nx > nz > ny and (nx-nz)/(nx-ny)=0.2 to 0.7, in which the above organic pigments are characterized by having at least one roganic pigment with a maximum absorption wavelength equal to or over 380nm and less than 550nm, and having at least another organic pigment with a maximum absorption wavelength equal to or over 550nm and equal to or below 780nm. The optical element has a function of being a phase-contrast element. When using a polarizing element having the above element, the optical element has the features of being capable of minimizing black luminance uniformly among the wavelength range of 450 to 700nm regardless of the wavelength, and by having less oblique light leakage, none or very few color-stain incurred upon the color of leakaged light.

Description

[Technical Field] The present invention relates to an optical element used for an image display device such as a liquid crystal display device and a viewing angle improving method using the polarizing film of the optical element. [Prior Art] The polarizing film is a necessary member in the liquid crystal display device, and can be obtained, for example, in the following manner. First, the polyethylene film immersed in a dichroic dye such as a water-soluble dichroic dye or a multi-moth ion is uniaxially stretched in an acid-removing/m aqueous solution, or a uniaxially stretched polyvinyl alcohol film. Then, a polyene structure is formed by a dehydration reaction to obtain a polarizing element. Next, the polarizing element is sandwiched between a surface treated with a protective film such as a cellulose triacetate film or a ring-smoke-smoke polymer with an adhesive, and the target polarizing plate is used. However, when two polarizing elements or polarizing films are used, when the individual absorption axes are arranged orthogonally, if the observation position is inclined in a direction different from the absorption axis direction in the front direction, the polarized light passing through the incident side is found. The polarized light of the element or the polarizing film is not completely absorbed by the emitting-side polarizing plate to cause so-called light leakage, that is, the polarizing element or the polarizing film has a problem of viewing angle dependency. This phenomenon particularly affects the viewing angle characteristics of liquid crystal display devices using various liquid crystal cells such as a vertical alignment (VA) type, a coplanar switching (Ips) change, and an optical compensation bend (0CB) type. In this patent, Patent Document 1 proposes a method of reducing the influence of the liquid crystal layer or the optical compensation member in the oblique field by specifying the optical constant of the retardation film to improve the black luminance in the oblique direction and to reduce the coloring. In addition, non-patent literature 4 323094

201200899 1 discloses a method for reducing the viewing angle dependence of a polarizing film by using a two-grazing phase difference plate. However, the method of Patent Document 1 does not completely improve the viewing angle dependency. Further, Non-Patent Document 1 can improve the viewing angle dependence of a specific wavelength by using the wavelength dependency of the retardation film. However, since the other wavelengths are still insufficient, the colored light leaks. Thus, the wavelength dependence of the effect of improving the viewing angle of the polarized light can be effectively improved by the method of Patent Document 2 or Non-Patent Read 2, but it is complicated to use a plurality of film layers. [Prior Art Document] [Patent Document 1] JP-A-2008-310064 [Patent Document 2] Japanese Patent No. 4137438 [Non-Patent Document] [Non-Patent Document] J. Chenetal., SID98DIGEST , P. 315 (1998) [Non-Patent Document 2] T. Ishinabe et al., SID00DIGEST, Ρ 1094 (2000) [Summary of the Invention] (The subject to be solved by the invention) As described above, although various kinds of improved polarizing elements or polarized light are available The method of viewing angle dependence of the film 'but can not solve the problem of the wavelength dependence of the viewing angle improving effect and the complicated use of the plural film at the same time. The present invention is directed to provide a film which does not use a complex & and which can improve the viewing angle dependence of a polarizing element or a polarizing film, and an optical element which reduces wavelength dependence at 5 323094 201200899. (Means for Solving the Problem) The present inventors have found that an optically anisotropic layer containing at least two kinds of dichroic dyes, a three-dimensional refractive index of nx > nz > ny, and an Nz coefficient of 〇2 to 〇7 is formed. The optical element (phase difference element) or the retardation film having the optical element on the transparent substrate is quite effective in solving the above problem. Further, in the present specification, the Nz coefficient represents a value of (nx_nz) / (nx_ny). For example, a polarizing film provided with the optical element is formed by forming the optical element on a polarizing film, and the polarizing film with the optical element is compared with a normal polarizing film because the optical element is disposed between the polarizing elements. When the arrangement is orthogonal to the absorption axes of the two polarizing elements, the above problem can be solved. In other words, even if the observation position is inclined in a direction different from the direction of each absorption axis in the front direction, the light transmission is lowered and a small amount of light is leaked. The present invention has been completed by the fact that it is not colored, and the dependence of the viewing angle of the polarizing film and the wavelength dependence of the viewing angle improving effect can be greatly reduced. That is, the present invention relates to the following invention. (1) An optical element comprising at least two kinds of organic dyes having an in-plane maximum refractive index of nx, and a refractive index of nx orthogonal to nx in the plane ny' relative to a plane perpendicular to a plane nz The three-dimensional refractive index is nx > nz > ny '(nx - nz) / (nx - ny) is a coloring and aligning optical anisotropic layer of 〇 · 2 to 0·7. (2) The optical element according to the above (1), wherein at least one of the organic dyes has a maximum absorption wavelength of 38 Å or more and less than 550 mn, and at least one organic dye has a maximum absorption wavelength of 550 nm or more and 780 nm. the following.

(3) The optical element according to the above (1) or (2), wherein the azo compound, the lanthanoid compound, the north ff. the northern compound, the quinophthalone compound, and the naphthyl a ^ 糸 compound or melocyanine compound. < ° Month The in-plane phase of the well described in any one of the above (1) to (3) and the optical anisotropic layer of 550 nm in length is measured at _nm. (4) A retardation film having any of the above (1) to (4) optical elements. (6) (7) A composite retardation film which is obtained by laminating a phase difference == a retardation film recorded by the above-mentioned optical element or the above (5). The composite phase difference m described in the above (6), and the other retardation film is of the type. Plate (negatiVeCplate) or positive C plate (Posit A-plate). (9) The light of any one of the above-mentioned (1) to (4) elements and a polarizing film. The phase difference film and the partial optical film described above are formed by laminating the film of the above (5). - An optical film which is formed by laminating a composite retardation film described in the above (6) or (7) and a polarizing film. The optical image described in the above (8) is formed by laminating the slow axis of the optical element and the absorption axis of the polarizing film. The optical film carried in the above (9) is formed by laminating the slow-dissipating film of the retardation film 323094 7 201200899 and the absorption of the polarizing film. (13) The optical element according to any one of the above (1) to (4), the retardation film of the above (5), or the above (6) or (7) At least one selected from the group consisting of the composite retardation film and the optical film described in any one of the above (8) to (12). (14) The image display device according to (13) above, which is a liquid crystal display device. (15) The optical element according to (a) above, wherein the optically anisotropic layer contains at least one of an organic dye having a maximum absorption wavelength of 380 nm or less and less than 550 nm and an organic dye having a maximum absorption wavelength of 550 nm or more and 780 nm or less. a layer of a layer formed by the composition of the oligobenzene compound and the compound represented by the following general formula (A):

Wherein X represents -0-CH2-ph-CH2-0---0-C0-ph-C0-0- or -NH-C0-ph-C0-NH-, and ph represents a wall acid group substituted For the stupid base, η represents the number of repetitions. (16) The optical element according to the above (15), wherein the organic dye having a maximum absorption wavelength of 380 nm or more and less than 550 nm is an azo compound represented by the following general formula (B) or a salt thereof.

8 323094 201200899 (wherein X represents no sulfonic acid group or carboxyl group, and Ri and R2 each independently represent a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, and η represents 1 or 2.) Further a 'maximum absorption wavelength The organic dye of 550 nm or more and 780 nm or less is a compound represented by the following general formula (C) or a salt thereof.

Q2i-N=N-fQ22-NSN-^Q23TN;N

Nhr21 N=N*~^ (S03H)rW\R24 -^23 (C) (wherein QZ1 is a naphthyl group having one or two sulfonic acid groups, a hydroxyl group or a C1 to C4 alkoxy group, q22 And q23 are each independently a phenyl or naphthyl group (these groups have one or two substituents, and the substituent is a group consisting of a C1 to C4 alkyl group, a C1 to C4 alkoxy group, a hydroxyl group, and a sulfonic acid group. One or two selected from the towels.), R21 is a hydrogen atom, a C1 to C4 alkyl group, an ethyl fluorenyl group, a benzamidine group, or a substituted or unsubstituted phenyl group, and each of R23 and R24 is independently a hydrogen atom. a hydroxyl group, a sulfonic acid group, a C1 to C4 alkyl group or a C1 to C4 alkoxy group, q represents 〇 or l'r represents 1 or 2. (Effect of the invention) The optical element of the invention has a function of generating a phase difference, It can be used as a phase difference element, and can be used as a retardation film by providing this optical element on a transparent substrate. In particular, the optical element having the phase difference 臈 on the polarizing film or the optical film having the phase difference 该 of the optical element (hereinafter referred to as a polarizing film with an optical element) is provided to reduce the position of the liquid crystal display device from the observation position. The light is obliquely slanted, and a small amount of light is not colored, and the effect of reducing the viewing angle of the polarizing film and the wavelength dependence of the viewing angle improving effect is 323094 9 201200899. In other words, the polarizing film provided with the optical element is disposed between the polarizing elements as compared with a normal polarizing film, and even when the absorption axes are arranged orthogonally, the observation position is directed to the absorption axis direction in the front direction. When tilting in different directions, the light transmission is reduced and a small amount of light is not colored, which greatly reduces the dependence of the viewing angle of the polarizing film and the wavelength dependence of the viewing angle improving effect. In this leaf, the polarizing film provided with the optical element is used in a liquid crystal display to improve the viewing angle characteristics of the liquid crystal display. [Embodiment] Hereinafter, the present invention will be described in more detail. The optical element of the present invention is composed of a biaxial layer defined as follows, which contains at least two types of organic pigments. The biaxiality referred to in the present invention means that the relationship of the secondary enthalpy refractive index nx > nz > ny is satisfied, and the Nz coefficient is 〇.2 to 〇. 7 ' is preferably 〇·3 to 〇. Here, η χ represents the in-plane maximum refractive index, ny represents a refractive index orthogonal to η χ in the plane, and η ζ represents a refractive index perpendicular to the plane. Further, the Νζ coefficient represents the value of (nx_nz) / (; nx_ny). If it is outside this range, there is a problem that the viewing angle improvement is insufficient when used in a liquid crystal display device or that coloring occurs in an oblique direction. In order to impart biaxiality, a method of stretching the crucible and a method of coating and drying the liquid crystal composition to form a coating film or a coating layer (hereinafter referred to as a coating film forming method) are mentioned. The method of extending the film, for example, the method described in JP-A-2006-291192, WO2006/117981, and the like. For example, the method of applying the liquid crystal composition to align the composition, for example, 曰本特表2009-540345, WO2010/020928, Japan 10 323094 3 201200899, JP-A-2006-48078, and JP-A-2006- The method described in '316138 and the like'. In the present invention, the latter alignment coating film forming method is preferred. In the method of coating the liquid crystal composition to align, it is preferred to use a liquid crystal composition exhibiting lyotropic liquid crystal, and the liquid crystal composition is composed of a supramolecular layer (SUpUram〇lecule). The supramolecules contain at least one of a plurality of cyclic organic compounds having a conjugated 7-lanthanide system and a functional group capable of forming a non-covalent bond between the supramolecules. Examples of the polycyclic organic compound having a liquid crystallinity include an oligobenzene compound, a bibenzimidazole compound, an acetonaphthoquinoxaline compound, a triazine compound, and the like. . Examples of the oligobenzene compound are shown in Table 丨, and examples of the bismuth imidazole compound are shown in Table 2. Examples of the acetamidine naphthacquinone compound are shown in Table 3. Further, examples of the trimorphine compound are shown in Table 4. Among the compounds having the above liquid crystallinity in the present month, an oligobenzene compound is preferred. Preferred compounds in the oligomeric compound are a stupid ring, a biphenyl ring, a naphthalene ring, a group of at least two rings, and at least one hetero atom selected through the group consisting of a nitrogen atom and a sulfur atom of an oxygen atom. Preferably, the benzene ring, the biphenyl ring or the Cai ring has a repeating acid group. For example, a compound represented by the above formula (9) can be mentioned. 323094 11 201200899 3—Τ Al

S〇3 Η η so (D) In the formula, Yl is, 0~, monovalent or grab, 'Y2 is a single bond, -0- or -NH-, and A2 independently represents benzene%, Caihuan or a benzene ring, a cross-acid group (the brain ο is substituted for the ring. Among these compounds, 4, 4, -(5, 5,-dioxydibenzo[b,d] porphin-3, (4,5,5'-dioxidodibenzo [b,d]thiene-3,7-diyl) dibenzenesulfonic acid). A liquid crystalline composition containing such compounds, for example, When the aligning process is performed, it is characterized in that the alignment satisfies the relationship of nx > nz > ny. [Table 1] 〇〇ho3s

So3h 4, 4' -(5-dioxydibenzo[b,d]thiophene-3,7-diyl)diphenylsulfonic acid ho3s

S〇3h naphtho[2,3-b:2' 3' -d]furan disulfonic acid

S〇3h 12H-benzo[b]cyanoquinone disulfonic acid ho3s

So3h two stupid and [b,i] dioxin disulfonic acid H〇3s 〆 12 323094

S 201200899

So3h benzo[b]naphtho[2',3' ··5,6]diindolo[2, 3-1]dioxane disulfonic acid

苊[1,2-b]benzo[g]quinoxaline disulfonic acid

9H-indolo[l,2-b]imidazo[4,5-g]quinoxaline disulfonic acid Η Ή \ V Μ ΛΛ Η

Η

OH 13 323094 201200899 [Table 3] (3-1)

RW

14 323094 201200899 (3-2)

Γ ho3s. Ί 0 νμν -RW Λ h2noc person ^^conh2

15 323094 201200899 (3-3)

Ho3s

16 323094 201200899 ' [Table 4]

r=ch3,c2h5,c3h7,c4h9

According to the invention, the liquid crystal composition of the human crystal composition by the liquid crystal compound and the post-it organic dye liquid is formed by forming a light layer formed on the substrate of the film or the like, and can be used as a financial optical component. The opposite direction may also be as described above: a liquid crystal (IV) polymer other than the liquid liquefaction a substance, or a plurality of crystalline k products. The bar represented by the liquid-impermeable liquid sheet is added by such ηχ, mr, for example, WO0/020928 (16 to 17 molecular liquid crystal polymer', which is specifically shown in Table 5, for example, showing polymerization of liquid crystallinity. The object 'adjustable optical element 323094 17 201200899 is preferred because of its relationship and durability. [Table 5] Table 5_1

Poly(2, 2'-disulfonic acid-4, 4'-benzidine to acesulfame)

Poly(2, 2'-disulfonic acid-4, 4'-benzidine p-benzoguanamine)

Poly(2-sulfonyl-1,4-phenylenesulfonyl p-benzoguanamine) poly(2,2'-disulfonic acid-4,4'-benzidinenaphthalene-2,6-dimethyl Guanamine

18 323094 201200899

Table 5-2

Poly(sulfonate-phenylene-1,2-extended ethyl-2,2'-disulfonate group)

Poly(disulfonate-extended biphenyl-1,2'-extended ethyl-2,2'-disulfonate-extended biphenyl) 19 323094

S 201200899 , so3h

Poly(2,2'-disulfonic acid biphenyl-2-sulfonic acid-1,4'-dioxyfluorenylbenzene) The liquid crystal polymer of the above rod-shaped molecule is preferably the following general formula (A) Compounds indicated.

Wherein X is -0-CH2-ph-CH2-0-, -0-C0-ph-C0-0- or -NH-C0-ph-C0-NH-, and ph represents a pair which may have a sulfonic acid group substitution Phenyl is extended and η represents the number of repeats. The liquid crystalline polymer has a weight average molecular number of from 1,000 to 200,000, preferably from about 2,000 to 100,000. Further, depending on the case, the weight average molecular number is about 3,000 to 70,000, or about 4,000 to 70,000. In order to form a coating liquid containing a liquid crystal composition containing two or more of the above organic dyes, a polycyclic organic compound having liquid crystallinity, and preferably a liquid crystal polymer, the solvent is usually contained. The solvent to be used is not particularly limited as long as it has excellent solubility and the composition is dissolved in a solvent, and examples thereof include water, alcohols, ethers, Cellosolve, and tracism. , dimethyl stagnation and so on. In the present invention, water is preferred from the viewpoint of use and the like. These can be used singly or in combination. 20 323094 201200899 > In addition, water-soluble solvents such as dimethylformamide, glycerin and ethylene glycol may be added. These additives can be used to adjust the drying rate of the solubility and the aqueous solution. The amount of the solvent is not particularly limited as long as it is a concentration at which the liquid crystal composition can be applied. For example, in the liquid crystalline composition containing a solvent, the solid concentration is usually from 5 to 50% by weight, preferably from 8 to 30% by weight, based on the total amount of the composition. In addition, use an E-type viscometer at 25. (: When measuring the viscosity of the liquid crystal composition of 200 to 1000 mPa · s, it is more suitable for the formation of liquid crystal. In the viscosity of this range, the MD direction is applied by shearing or coating, and the liquid crystal alignment is It is preferable that it is perpendicular to the MD direction. The organic dye of at least two types used in the optical element of the present invention may, for example, be an azo compound, an onion@Kun-based compound, a flower-based compound, or an indole-yellow compound. The naphthoquinone-based compound or the merocyanine-based compound has no problem even if it is a dye of the same type or a different type. Usually, it is preferably a compound of the same kind, and more preferably an azo-based compound which exhibits dichroism. Application of functional pigments (Into Jiang Zhenghao, CMC Publishing) azo compounds described on pages 98 to 100, CI Direct. Yellow28, CI Direct. Yellow44, CI Direct. 0range26, CI Direct. 0rangel07, CI Direct. 0range71, C. I· Direct·Red2, C·I. Direct. Red31, CI Direct. Red79, CI Direct.

Red247, C.I. Direct. Green80, C. I. Direct. Blue202, C. I. Direct. Blackl7, C. I. Direct. Blue83, C. I. Direct.

Orange 39, C.I. Direct. Red79, C. I. Direct. Red81, C.I. Direct. Yellowl2, C.I. Direct. Blue67, C. I. 21 323094 201200899

Direct. Reci39, C.I. Acid Red37, C. I. Direct. Green59, C. I. Direct. 0range72, C. I. Direct. Red89, C. I. Direct.

Red 83 ' CI Direct. Violet 48 > CI Direct. Blue 90 and JP-A-2001-33627, JP-A-2002-296417, JP-A-2003-215338, WO2004/092282, and JP-A-2001 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. An organic dye or the like described in Japanese Patent No. 2622748 and Japanese Patent No. 3963979. At least two organic dyes used to form the optical element or the retardation film of the present invention are preferably at least one of the organic dyes having a maximum absorption wavelength of 380 nm or more and less than 550 nm, and at least one of the organic dyes has a maximum absorption wavelength. It is 38 nm or more and 780 nm or less. More preferably, at least one of the organic dyes (first pigments) has a maximum absorption wavelength of 430 nm or more and 470 nm or less, and at least one of the organic dyes (second pigments) has a maximum absorption wavelength of 570 nm or more and 630 nm or less. The first coloring matter may, for example, be an organic material described in C.I. Direct. 〇range39, C.I. Direct. 0range71, C.I. Direct. 〇range26, C.I. Direct. Orangel07 and WO2007/138980. Among them, an azo compound represented by the following general formula (B) or a salt thereof is preferred. 22 323094

S 201200899

Wherein X is a thiol group or a fluorenyl group, and Ri and R2 each independently represent a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, and η represents 1 or 2.

The second coloring matter may, for example, be C.I. Direct. Blue202, C.I.

Direct. Blackl7, C.I. Direct. Blue83, C.I. Direct

An organic dye described in Green 51, JP-A-2001-33627, and Japanese Patent No. 3963979 (0022 to 0027). Preferred examples of the dye include the compounds represented by the following general formula (C) or salts thereof. Q21-N: N+Q22-N=N^-Q23

Latch 23 ^24 where Qu is a naphthyl group having one or two sulfonic acid groups, having a hydroxyl group or a ci (C) to C4 alkoxy group, and Q22 and Q23 are each independently a phenyl or anthracene group (these The group has one or two substituents selected from C1 to a group consisting of an alkyl group, a C1 to C4 methoxy group, and a hetero group.) 'r21 is a ruthenium atom, CuC4 alkyl, ethyl, bromo, or substituted or unsubstituted phenyl, R23, R24 are each independently a nitrogen atom, a base group, a acid group, a C1 to C4 alkyl group or a C to C4 oxygenate. Base, q represents 〇 or 1, and r represents 1 or 2. By using a dye containing two or more kinds of extremely large wavelength phases (four), the present moonlight photonic device can exhibit a remarkable excellent effect. For example, the polarizing film provided with the optical element of the present invention 323094 23 201200899 is disposed between the polarizing elements as compared with a normal polarizing film, and is disposed between the polarizing elements and the respective absorption axes, even if the viewing position is absorbed in the front direction. The wheel direction is inclined in different directions, and the light transmission is less and a small amount of light is not colored, which can greatly reduce the dependence of the viewing angle of the polarizing film and the wavelength dependence of the viewing angle improvement effect. The total concentration of the above organic dyes is added so as not to greatly reduce the transmittance. It is preferably 0.01 to 10% by weight, more preferably 0 to 5% by weight, still more preferably 3% by weight based on the total amount of the solid matter of the coating liquid. Further, the ratio of the first coloring matter to the second coloring matter may be appropriately selected. For 1 part by weight of the first coloring matter, the second coloring matter is 〇1 to 1% by weight, preferably 0.2 to 5 parts by weight, more preferably 0.5 to 2 parts by weight. 5重量份的比例。 By weight, the best is 〇 · 7 to 1. 5 parts by weight. When the optical τ of the present invention is used as a phase difference test, the liquid positive composition of the polycyclic organic compound having a liquid crystallinity and the organic dye containing the upper enamel is preferably a compound containing the liquid crystalline polymer. The liquid crystal site is formed by coating a transparent substrate, and forming a retardation film by forming an optical foreign matter on the substrate. Further, the application of the liquid crystal composition to the optical anisotropic layer having the orientation of the original == alignment can also be used as the ^(4) bias region. In addition, according to the same situation, it can also form the above-mentioned alignment on the same type of base material. == 学 Μ 四 四 四 四 四 四 四 四 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 M M M M M M M M M M M The coating method is not limited to the uniform coating, but also the slanting plate coating (siid ( 323094 s 24 201200899 coater), slit die coating (si〇t die coater), Bar coater, rod coater, roll coater, curtain coater, spray coater ), nozzle die coating (lip die c〇ater), vacuum die coater, gravure coater, reverse gravure c〇ater, micro gravure coating (micro gravure coater) or the like, which is applied to a substrate by a suitable coater and a method of stretching on a metal can. Preferably, a die coating or a gravure coating is used, and the gravure coating and the straightening roller are used. (sm〇〇thing roll) is also effective. The drying method is not particularly limited, and it can be dried naturally and decompressed. , drying by heating, drying under reduced pressure, etc. The drying method of any drying device such as an air circulation drying oven or a heat roller can be used as a heating and drying means. The preferred drying method is at a low temperature and the relative humidity is 60% or less. The retardation film of the present invention generally uses a transparent plastic substrate or glass as the substrate to be used, preferably a plastic substrate. The plastic substrate used in the present invention may be acrylic resin, polycarbonate resin or epoxy. Examples of the resin, the cellulose resin, and the like include cellulose triacetate (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (pEN), and para-type polystyrene (sps). ), polyphenylene sulfide (pps), polycarbonate (10), polyacrylic acid vinegar (pAr), polysulfone (PSF), polypyretic (PES), polypyridinium (pEI), cyclic polyolefin, poly The imine (PI) or the like is preferably TAC. The thickness of the substrate is not particularly limited except for the purpose of use, and is generally in the range of the mouth of the phantom. Further, in order to adjust the wettability of the composition used in the present invention. , preferably 323094 25 201200899 for each film table Surface treatment such as corona treatment or plasma treatment (Piasma) treatment, primer treatment, primer treatment, etc. The optically anisotropic layer or retardation film of the present invention is measured at a wavelength of 55 〇 nm. The internal phase difference is 130 to 300 nm, preferably 150 to 270 nm, and more preferably 180 to 250 nm. The thickness of the optically anisotropic layer depends on various optical parameters such as the liquid crystal cell and the in-plane phase difference, and thus cannot be generalized. It is 0.1 to 10 μm. The better is 〇.1 to 2em. The above optically anisotropic layer can be treated to improve the water resistance after film formation. For example, a method in which a chelating agent is substituted with a poorly soluble group which is insoluble or poorly soluble in water is used. Examples of the chelating agent include salts of metal ions such as Ni2+, Ca2+, Fe3+, Cu2+, Zn2+, Al3+, Pd2+, Cd2+, Pb2+, Sn2+, Co2+, Mn2+, Ba2+, and Ce3+, or salts of organic amines. These chelating agents may be used singly or in combination of two or more kinds in any ratio. Further, other methods may be used to provide a protective layer on the optical anisotropic layer. The material to be used for the protective layer is not particularly limited, and examples thereof include a polyurethane resin, an epoxy resin, and an acrylic resin. These may be used alone or in combination of two or more. It is preferably a hydrophobic material, more preferably a polyamine (tetra) grease. The resin which is excellent in flexibility does not break the alignment state of the optical anisotropic layer, and can be laminated on the optical anisotropic layer. The above method of using a chelating agent and a method of providing a protective layer can be used in combination. In order to obtain the characteristic value of the phase difference film of the present invention for I, an optical anisotropic layer can be laminated on the substrate. At this time, the hydration treatment using the chelating agent and the hydration treatment of the protective layer can be carried out in each layer, or in the all-optical anisotropic layer 323094

S 26 201200899 After the layering. The film film can be laminated with the polarizing film or other phase difference sounds such as ^ 2 and the retracting axis 3 . If it is desired to accumulate θ as shown in the first figure, the optically anisotropic layer 2 is formed by applying directly to the bias 1 . 2 Figure 'Silk (4) 2 in the phase difference film of the New Zealand, into the layer side through the acrylic adhesive 5 and the polarizing film} or phase difference 臈 layer. Or the optically anisotropic layer 2 formed on the 3®' substrate 7 may be bonded to a polarizing film or other retardation film via a sturdy adhesive, and the substrate 1 2 3 4 = away from The optical anisotropic layer is transferred to the polarizing film i or other retardation film. The retardation film of the present invention can be used in combination with other retardation films, for example, in combination with a negative C plate or a positive c plate. The polarizing film to which the optical element of the present invention is attached is used to form a polarizing film, and the polarizing film to be used is generally used. The polarized yak (polarizer) used in the polarizing film is an absorption type polarizing element that does not limit the light polarization of a specific direction and has a specific direction of light in a specific direction, as long as it has an effect of polarizing light emitted from a light source, that is, no 27 323 094 1 . A polarized reflective polarizing element can be used. In the absorbing type 3 polarizing element, for example, a polarizing element obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol-based film containing a dichroic dye 4 such as a dye or a polyvalent iodide ion is uniaxially applied to the polyvinyl alcohol film. Before and after the stretching, acid dehydration is formed to form a polyene, a polarizing element obtained by the structure, and a dichroic dye solution capable of exhibiting a liquid crystalline state is coated on the alignment film of the fixed direction alignment treatment, and then the solvent is removed. The obtained polarizing element or the like. On the other hand, the reflective polarizer 201200899 may be, for example, a polarizing element formed of a multi-layered multi-layered multilayer body, a polarizing element having a selective reflection region, and a 1/4 wavelength plate combined with a polarizing element and a substrate. A polarizing element of a fine metal grid (wire gird) or the like is provided thereon. In order to obtain a further effect of the present invention, it is preferred to use a hydrophilic polymer film such as a polyvinyl alcohol film containing a dichroic dye such as a dye or a polyvalent iodide ion, which is excellent in polarizing characteristics as a polarizing element, and uniaxially stretched. The obtained polarizing element is a polarizing element obtained by dehydrating acid to form a polyene structure before and after uniaxial stretching of the polyethylene glycol film. The above polarizing element can be manufactured by a conventional method. For example, in the case of a polarizing element formed of a polyvinyl alcohol-based film containing a dichroic dye such as a dye or a polyvalent iodide ion, first, the polyvinyl alcohol-based film is swollen with warm water or the like, and then impregnated with the dissolving dichroic dye. The dyeing tank dyes the film, and then uniaxially stretches and dries in a tank containing a crosslinking agent such as boric acid and shed sand to obtain the polarizing element. The dye used for the dyeing is exemplified by the magnetic-molybdate potassium aqueous solution and the "application of functional dyes" (into Jiang Masahiro, CMC Publishing), azo compounds described in pages 98-100, CI Direct. Yellow 12, CI Direct. Yellow 28 ' CI Direct. Yellow 44 > CI Direct. Orange 26, CI· Direct. Orange 39, CI Direct. Orange 107, CI Direct. Red 2, C. I. Direct. Red 31, C. I· Direct. Red 79, C. I. Direct. Red 81, C·I· Direct. Red 247, CI Direct. Green 80, CI Direct. Green 59, and Sakamoto Kaikai 2001-33627, Japan Special Open 2002-296417, Japan Japanese Patent Laid-Open No. 2003-215338, WO2004/092282, Japanese Patent Laid-Open No. 2001-0564112, Sakamoto Kaikai 2001-027708, Japanese Patent Laid-Open No. 11-218611, Japanese Special Open 28 323094 201200899, Ping 1 Bu 218610, and Japanese Special Open 6 (M56759) The organic dyes described in Japanese Patent Publication No. 2/27 and Japanese Patent No. 2622748. Some of the dichromatic dyes include, in addition to the free acid, alkali metal salts (for example, Na 2 : salts and Li salts). , ammonium salt, amine salt, or mixed salt (10) such as Cu di Lh wide complex and C° Thereof) and the like. The performance of the polarizing element can be adjusted by the dichroism of the pigment and the stretching ratio at the time of extension. = inventing an optically anisotropic layer (optical element) or a retardation film of the present invention, or an anisotropic layer (optical element) or a composite retardation film of the retardation film and other retardation film such as liquid helium S In the optical path of the image display device, for example, the liquid crystal panel member is combined with the polarizing plate at least on the liquid crystal single (four) side or the like. The image display device of the present invention, for example, a liquid crystal display device. There are various modes depending on the liquid crystal cell used, regardless of the film. It is possible to use a polarization compensation VA (vertical alignment) type, a 1PS (coplanar switching) type, an 0CB (light two-member bending) type, and a TN (twisted nematic) type provided with the optical anisotropic layer (optical element) of the present invention. The present invention can be used in both STN (super-twisted nematic) type liquid crystal display devices. The Nz phase difference of the optical anisotropic layer (optical element) or each retardation film may be adjusted according to its respective characteristics. [Implementation, j] The present invention will be described in more detail by way of examples, but the invention is not limited thereto. Further, in the examples and examples, the parts represent parts by weight, and % represents % by weight. [Compound Example] 29 323094 201200899 The following compounds described in JP-A-2009-540345 13. 6 parts, H〇3s

So3h 2. 4 copies of the following description in W02010/020928

The following organic dyes of 0. 08 parts, as described in the publication of the above-mentioned organic dyes (ci. Direct·Orange 39), 0.08, and Japanese Patent No. 3963979,

They were uniformly mixed to prepare a solution of about 16% solids. The viscosity of the solution was determined to be 330 mPa·s at 25 ° C using an E-type viscosity meter. In the same manner as in the mixing example 1, a solution of a solid % was prepared except that 0.08 parts of C.I. Direct. Blue 67 was used instead of 0.08 parts of the above organic dye described in Japanese Patent No. 3963979. The viscosity of the solution is at 25 for the E-type viscosity meter. (: 330 mPa · s 〇 约 about 16 is determined as 323094 30 201200899 'Compatible Example 3 • In the above compounding example 1, except that the above organic dye is not blended C. I.

A solution of about 16% of a solid matter was prepared in the same manner as in the mixing example 1 except for the above-mentioned organic dyes described in Japanese Patent No. 3963979. The viscosity of the solution was determined to be 330 mPa·s at 25 ° C using an E plastic viscosity meter. In the above-mentioned compounding example 1, a solution of about 16% of a solid matter was prepared in the same manner as in the mixing example 1 except that C.I. Direct. Orange 39 was not blended with the above organic dye. The viscosity of the solution was determined to be 330 mPa·s at 25 ° C using an e-plastic viscometer. Example 1 The solution obtained in the mixing example 1 was dried on an iodine-based polarizing plate la (trade name: SKN, manufactured by Polatechno Co., Ltd.), and then coated with 1·〇"m and using a wire bar (#i 〇) The shearing force is applied in the direction of the ribs and blown dry by an air compressor. Next, a 1 〇% aqueous solution of lanthanum nitrate was sprayed on the coated surface, and air-dried again by an air compressor to form an optical anisotropic layer, that is, the production of a polarizing film (optical film) with the optical element of the present invention was completed. (Example 2) A polarizing film to which the optical element of the present invention was attached was produced in the same manner as in Example 1 except that the solution prepared by the mixing of the four (4) generations prepared in the mixing example 2 was used. Example 3 On the surface of the cellulose triacetate (10) film, the solution prepared by the compounding method of 323094 31 201200899 1 was coated to have a thickness of 1.0/m after drying, using a metal wire rod (#10). The MD direction is sheared and blown dry by an air compressor. Next, a 10% aqueous solution of lanthanum nitrate was sprayed on the coated surface, and air-dried again with an air compressor to complete the production of a retardation film having an optically anisotropic layer on the film. The TAC surface of the retardation film and the iodine-based polarizing plate la (trade name: SKN, manufactured by the company Pol a techno) are adhered by acrylic so that the slow axis of the retardation film is orthogonal to the absorption axis of the polarizing plate. The agent 5 is bonded to complete the production of the film. Comparative Example 1 An iodine-based polarizing plate la (trade name: SKN, manufactured by Polatechno Co., Ltd.) having no optical anisotropic layer used in Example 1 was used as it was. Comparative Example 2 The same procedure as in Example 1 was carried out, except that the solution prepared in the mixing example 3 was used instead of the solution prepared in the same manner as in Example 1, to obtain a polarizing film having a comparative optical anisotropic layer. Comparative Example 3 The same procedure as in Example 1 was carried out, except that the solution prepared in the mixing example 4 was used instead of the solution prepared in the same manner as in Example 1, to obtain a polarizing film having a comparative optical anisotropic layer. The nx, ny, nz and Nz coefficients of the respective optically anisotropic layers obtained above are as follows. Nx Ny nz Nz coefficient Example 1 1. 80 1. 60 1. 73 0.38 Example 2 1. 80 1. 60 1. 73 0. 35 32 323094 s 201200899 Example 3 1. 81 1. 60 1. 73 0 38 Comparative Example 1 (no optical anisotropic layer) Comparative Example 2 1. 80 1. 59 1. 73 0. 33 Comparative Example 3 1.80 1.60 1.73 0.35 Further, the surface of the optical anisotropic layer measured at a measurement wavelength of 55 Onm The internal phase difference is as follows. Example 1 205 nm Example 2 205 nm Example 3 215 nm Comparative Example 1 (no optical anisotropic layer) Comparative Example 2 195 nm Comparative Example 3 20 Onm <Optical characteristics: black luminance in an oblique direction> As shown in Fig. 4, The optical anisotropic layer side 2 of the optical film (the polarizing film with the optical element of the present invention) formed by the optically anisotropic layers obtained in Examples 1 to 2 and Example 3 was made of an acrylic adhesive 5 (trade name) PTR-2500, manufactured by Nippon Kayaku Co., Ltd.) is bonded to one side of the glass plate 8. The other side of the glass plate 8 is also laminated with an iodine-based polarizing plate 5 and an iodine-based polarizing plate la (trade name: SKN, manufactured by Polatechno Co., Ltd.) so that the absorption axes are orthogonal to each other, that is, the laminated layer for optical property test is completed. Production of samples (optical systems). Further, Comparative Examples 1 to 3 were also produced in the same manner as a laminated sample (optical 糸) for optical property test. As shown in Fig. 6, the laminated sample having the above configuration is measured from a polar angle of 0°, an azimuth angle of 0°, a polar angle of 50°, and an azimuth angle of 45° to obtain a visual sensitivity correction positive 33 323094 201200899 cross transmittance Yc (〇 , 〇), Yc (5〇, 45). The transmittance was measured using a spectrophotometer (U-4100, manufactured by Hitachi Lighting Co., Ltd.). The black luminance in the oblique direction is preferably as small as the Yc value. Fig. 7 shows the orthogonal transmittance waveforms of Example 1 and Comparative Examples 1 to 2. Further, Table 6 shows the results of the examples 丨 to 3 and the results of the comparative examples 1 to 3 using the liquid crystal panel having the optical element of the present invention, and it can be understood from Fig. 7 that the orthogonal transmittance is not in the range of about 450 to 700 wavelengths. It is as low as the wavelength, and as is known from Fig. 6, the black luminance value in the oblique direction is low. In addition, it is known that the oblique direction is also not colored or the coloring is very small. <Optical characteristics: coloring in the oblique direction> The liquid crystal panel was taken out from the liquid crystal display device of the liquid crystal cell containing the IPS mode [the liquid crystal TV product name "W000j" manufactured by Hitachi, Ltd.), and the optical film disposed on the backlight side of the liquid crystal cell was removed. a part, and the glass surface (inside and outside) of the liquid crystal cell is washed. The optical anisotropic layer side 2 of the film formed by the optically anisotropic layers obtained in Examples 1 to 3 is made of an acrylic adhesive 5 (trade name). PTR-2500, manufactured by Nippon Kayaku Co., Ltd.) is bonded to the backlight side of the liquid crystal cell, and the slow axis of the optical anisotropic layer and the retardation film is bonded in parallel with the longitudinal direction of the liquid crystal. The absorption axis of the polarizing plate (trade name: SKN, manufactured by Polatechno Co., Ltd.) of the film formed by the optically anisotropic layer obtained in Example i and Example 2 is orthogonal to the absorption axis of the unit-side polarizing plate. The obtained liquid crystal panel was used for the test. Further, Comparative Examples 1 to 3 were also fabricated into a test liquid crystal panel in the same manner. The obtained liquid crystal panel for test was placed on a backlight to form a liquid crystal display device. The display device displays black surface day 'backlight in a dark point in the true 323094

S 34 201200899 ^ After 30 minutes, observe the degree of coloration in a visually oblique direction (azimuth angle 45°, polar angle 50°). Table 6 shows the results regarding Examples 1 to 3 and Comparative Examples 1 to 3. ◎: no coloring 〇: a little coloring △: coloring X: large-area coloring The above evaluation results are shown in Table 6 below (Table 6) Yc(0,0) Yc(50,45) Color evaluation of oblique direction Example 1 0. 01% 0. 20% ◎ Example 2 0. 01% 0. 27% 〇 Example 3 0.01% 0.21% ◎ t匕 Comparative Example 1 0. 01% 0.47% X Comparative Example 2 0.01% 0.30% △ Comparative Example 3 0. 01% 0. 028% Δ [Industrial Applicability] By using an optical film having the optical element of the present invention, it is possible to use a complex retardation film in a wavelength range of about 450 to 700 nm. Regardless of the wavelength effect, the orthogonal transmittance can be suppressed to a low range. Further, it is possible to suppress the black luminance in the oblique direction while suppressing the coloring in the oblique direction or the coloring is extremely small, so that it is extremely useful as an optical element. [Simple description of the drawings] 35 323094 201200899 Fig. 1 is a view showing a structure in which a polarizing film is bonded. Fig. 2 is a view showing a structure in which a polarizing 臈 is attached. Fig. 3 is a view showing a structure in which a polarizing film is bonded to each other. Fig. 4 is a diagram showing the composition of the sample in the oblique direction black luminance. Fig. 5 is a diagram showing the composition of the sample in the oblique direction black luminance. Fig. 6 is an explanatory view of the measurement direction of the oblique direction. Figure 7 is a polar angle of 50. Azimuth angle 45. A graph of the orthogonal transmittance waveforms. [Main component symbol description] 1 Polarizing film la Polarizing film 2 Optical anisotropic layer 3 Absorption axis 4 Fast axis 5 Adhesive 6 Substrate 7 Release substrate 8 Glass plate 9 Measurement sample 10 Azimuth angle 0 11 Polar angle φ 12 Front direction (0,0)=(0 0) 13 φ is 0 to 180. Shaft 36 323094

Claims (1)

201200899 * VII. Patent application scope: The optical X• part system consists of at least two kinds of organic pigments, the maximum refractive index in the plane is nx, and the refractive index orthogonal to nx in the plane is 叮, relative to the surface When the refractive index in the vertical direction is nz, the three-dimensional refractive index is η χ > nz > ny, (nx - nz) / (nx - ny) is 0. 2 to 〇 7 of the colored and aligned optical anisotropic layer Composition. 2. The optical component according to claim 1, wherein the organic dye has a maximum absorption wavelength of 38 〇 nm or more and less than 550 nm, and at least one organic dye has a maximum absorption wavelength of 550 nm. Above, below 780 nm. 3. The optical element according to claim 1, wherein the organic dye is an azo compound, a quinone compound, an anthraquinone compound, a quinone yellow (qu i nophtha 1 one ) compound, naphthalene A lanthanide compound or a merocyanine compound. 4. The optical component according to claim 1, wherein the in-plane retardation value of the optically anisotropic layer at a wavelength of 550 nm is from 13 〇 nm to 3 〇〇 nm. A retardation film having the optical component described in claim 1 of the patent application. A composite retardation film which is obtained by laminating an optical element according to any one of claims 4 to 4 or a phase difference 所述 and other retardation film described in claim 5 . 7. The composite retardation film according to claim 6, wherein the other retardation film is a negative C plate or a positive C plate. ’ 323094 1 201200899 8. An optical film consisting of an optical element and a polarizing film as described in the section of the patent application. 9. An optical film is made up of a layer of ginger film and a polarizing film laminated in the scope of the patent application. 10. The optical enthalpy is a composite retardation film and a polarized entangled layer of the sixth or seventh aspect of the patent application. U. The optical film according to claim 8 is formed by laminating the slow axis of the aperture element and the absorption axis of the polarizing film. 12 is as described in claim 9 The optical film is a layered image display device in which the slow axis of the phase and the absorption axis of the polarizing film are orthogonal to each other, and the image display device of the patent image is provided by the first patent of the patent. The optical element, the phase difference film of the fifth item of the fourth item, the double phase difference film described in the sixth or seventh aspect of the patent application, and the light of any of the claims 8 to 12 At least one selected from the group consisting of membranes. 14. ^ The image described in item 13 of the patent application (4) is mounted as a liquid crystal display device. The optical component according to claim 1, wherein the optical anisotropic layer is composed of an organic dye having a maximum absorption wavelength of 380 ηηη or more and less than 55 〇 nm and a maximum absorption wavelength of 55 〇 nm or more. A layer formed by at least one of an organic dye of 78 〇 nm or less, an oligobenzene compound, and a composition of a compound represented by the following general formula (A): 2 323094 S x 201200899 (A) Formula t ' X represents -〇-CH2-ph-CH2-0-, -0-C0-ph-CO-0, or -NU-CO-ph-CO-NH-, ph indicates that it may have a sulfonic acid The base substitution ' η represents a repeat number. The optical element according to claim 15, wherein the organic dye having a maximum absorption wavelength of 380 nm or more and less than 550 nm is an azo compound represented by the following general formula (B) or a salt thereof. (wherein χ represents a sulfonic acid group or a carboxyl group, and R1 and Rz each independently represent a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, η represents 1 or 2), and further a 'maximum absorption wavelength is 55 〇 nm. The above organic dye of 78 〇 nm or less is a compound represented by the following general formula (C) or a salt thereof, and Q2rN=N-(-Q22-NN-^-Q23 ^23 R24 (wherein 'Q21 is a naphthyl group having one or two sulfonic acid groups and having a hydroxy group to a C1 to C4 alkoxy group, 'q22, q23 are each independently a phenyl or naphthyl group (these The substituent has one or two substituents which are one or both selected from the group consisting of a C1 to C4 alkyl group, a C1 to C4 alkoxy group, a hydroxyl group and a sulfonic acid group, and R21 is a hydrogen atom. , C1 to C4 alkyl, ethyl hydrazino, phenyl fluorenyl, or substituted or unsubstituted phenyl, r23, 323094 201200899 R24 are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, a Cl to C4 alkyl group or a C1 To C4 alkoxy, q represents 0 or l, and r represents 1 or 2). 323094 S