WO2016186196A1 - アゾ化合物及びそれらを含有する染料系偏光膜並びに偏光板 - Google Patents
アゾ化合物及びそれらを含有する染料系偏光膜並びに偏光板 Download PDFInfo
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- WO2016186196A1 WO2016186196A1 PCT/JP2016/064988 JP2016064988W WO2016186196A1 WO 2016186196 A1 WO2016186196 A1 WO 2016186196A1 JP 2016064988 W JP2016064988 W JP 2016064988W WO 2016186196 A1 WO2016186196 A1 WO 2016186196A1
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- Prior art keywords
- group
- dye
- polarizing plate
- azo compound
- polarizing film
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- 0 CCCCCOC(C(NC(NC(C=C[C@](C1)N=NC(C(OCCCC*)=C2)=CC(CC)[C@@]2N=NC2=C(C(CC(*)=C3)O)C3=CC(*C*)C2)=C1OCCCC*)O)=CC1)=CC1N=NC(C=C(*(C1)N=N[C@@]2c(c(O)cc(*)c3)c3C=C(*)C2)O*C)=C1OCCCC* Chemical compound CCCCCOC(C(NC(NC(C=C[C@](C1)N=NC(C(OCCCC*)=C2)=CC(CC)[C@@]2N=NC2=C(C(CC(*)=C3)O)C3=CC(*C*)C2)=C1OCCCC*)O)=CC1)=CC1N=NC(C=C(*(C1)N=N[C@@]2c(c(O)cc(*)c3)c3C=C(*)C2)O*C)=C1OCCCC* 0.000 description 3
- DILRGJHTNZOQNK-UHFFFAOYSA-N C(C1)C2C1COC2 Chemical compound C(C1)C2C1COC2 DILRGJHTNZOQNK-UHFFFAOYSA-N 0.000 description 1
- AYFRWOJFFCXYTQ-MRCUWXFGSA-N Cc1cc(/N=N\c2ccc(cc(cc3S(O)(=O)=O)S(O)(=O)=O)c3c2)c(C)cc1N Chemical compound Cc1cc(/N=N\c2ccc(cc(cc3S(O)(=O)=O)S(O)(=O)=O)c3c2)c(C)cc1N AYFRWOJFFCXYTQ-MRCUWXFGSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N c(cc1)cc2c1cccc2 Chemical compound c(cc1)cc2c1cccc2 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
- C09B43/124—Preparation of azo dyes from other azo compounds by acylation of amino groups with monocarboxylic acids, carbamic esters or halides, mono- isocyanates, or haloformic acid esters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to a novel azo compound, a dye-type polarizing film containing them, and a polarizing plate.
- a polarizing plate having a light transmission / shielding function is a basic component of a display device such as a liquid crystal display (LCD) together with a liquid crystal having a light switching function.
- LCD liquid crystal display
- Applications of this LCD include small computers such as calculators and watches in the early days, notebook computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring devices. Further, it can be applied to a lens having a polarization function, and has been applied to sunglasses with improved visibility, and in recent years to polarized glasses compatible with 3D televisions. Since the application of the polarizing plate as described above is widespread, it is used under a wide range of conditions from low temperature to high temperature, low humidity to high humidity, and low light quantity to high light quantity. There is a need for a polarizing plate having a property.
- polarizing plates are used for polarizing film base materials such as stretched and oriented polyvinyl alcohol or derivatives thereof, polyene film formed by dehydrochlorination of polyvinyl chloride film or dehydration of polyvinyl alcohol film, and oriented. It is produced by dyeing or containing iodine or a dichroic dye. These are substances that greatly affect the polarization characteristics and durability of the polarizing plate. Although an iodine polarizing film using iodine is excellent in polarization performance, it is weak against water and heat, and has a problem in durability when used for a long time at high temperature and high humidity.
- a polarizing film made by adsorbing and orienting several kinds of dyes on a polymer film if there is light leakage (color leakage) of a specific wavelength in the visible light wavelength range, the polarizing film is attached to the liquid crystal panel. In such a case, the hue of the liquid crystal display may change in the dark state. Therefore, when a polarizing film is mounted on a liquid crystal display device, a neutral color in which several dyes are dyed or contained in a polymer film is used to prevent discoloration of the liquid crystal display due to color leakage of a specific wavelength in the dark state.
- the orthogonal transmittance (orthogonal transmittance) in the wavelength region of the visible light region must be uniformly reduced.
- a polarizing plate having no change in the degree of polarization is also required because it becomes a high temperature and high humidity environment in a summer car.
- iodine-based polarizing plates with good polarization performance and neutral gray were used.
- iodine-based polarizing plates have a problem that light resistance, heat resistance, and moist heat resistance are not sufficient as described above.
- a dye-based neutral gray polarizing plate containing several kinds of dichroic dyes or containing dyes has been used.
- the dye-based neutral gray polarizing plate is generally used in combination with red, blue, and yellow dyes that are the three primary colors of light.
- the polarizing performance of the dye-based neutral gray polarizing plate is not sufficient. Therefore, it was necessary to develop a dichroic dye having good polarization performance for each of the three primary colors.
- the characteristic of the dye system is that, as described above, in order to control the components of the three primary colors of light, each corresponding dye is dyed or contained.
- a light source used in a liquid crystal display panel in recent years includes a cold cathode tube method or an LED method, and the wavelength of the light source emitted from the light source differs depending on the method. Therefore, in developing a dichroic dye having good polarization performance, it is particularly important to design a dichroic dye having an absorption wavelength that matches the wavelength of the light source.
- Examples of the dye used in the production of the dye-based polarizing film as described above include water-soluble azo compounds described in Patent Documents 1 to 5, for example.
- a polarizing film and a polarizing plate containing a specific azo compound or a salt thereof have excellent polarizing performance, moisture resistance, heat resistance, and light resistance.
- the present invention was completed.
- A is a hydrogen atom, a hydroxy group, a sulfo group having 1 to 5 carbon atoms and / or a naphthyl group having a sulfo group, and at least one of R 1 to R 4 is independently a sulfo group.
- a C 1-4 alkoxy group having a group, and the other R 1 to R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms)
- An azo compound represented by ⁇ 2> In the above formula (1), the other R 1 to R 4 are each independently a hydrogen atom, a methyl group or a methoxy group, the azo compound or a salt thereof according to ⁇ 1>, ⁇ 3> (A) R 1 is a C 1-4 alkoxy group having a sulfo group, (b) R 3 is a C 1-4 alkoxy group having a sulfo group, or (c) R 1 and R Azo compound or a salt thereof according to ⁇ 1> or ⁇ 2>, wherein 3 is an alkoxy group having 1 to 4 carbon atoms each independently having a sulfo group, ⁇ 4> In the above formula (1), the azo compound or a salt thereof according to
- R 7 to R 10 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and x is an integer of 1 to 3)
- An azo compound represented by ⁇ 7> In the above formula (3), R 7 to R 10 which are not alkoxy groups having 1 to 4 carbon atoms having a sulfo group are each independently a hydrogen atom, a methyl group or a methoxy group.
- a compound or a salt thereof, ⁇ 8> (A) R 8 is a C 1-4 alkoxy group having a sulfo group, (b) R 10 is a C 1-4 alkoxy group having a sulfo group, or (c) R 8 and R The azo compound or a salt thereof according to ⁇ 6> or ⁇ 7>, wherein 10 is an alkoxy group having 1 to 4 carbon atoms each independently having a sulfo group, ⁇ 9>
- R 6 is a hydrogen atom and x is 2, The azo compound or a salt thereof according to any one of ⁇ 6> to ⁇ 8>, ⁇ 10>
- the azo compound or a salt thereof according to any one of ⁇ 6> to ⁇ 9> wherein the alkoxy group having 1 to 4 carbon atoms having a sulfo group is a 3-sulfopropoxy group, ⁇ 11>
- a dye-based polarizing film comprising a polar
- the azo compound or salt thereof of the present invention is useful as a dye for a polarizing film.
- the polarizing film containing these compounds has high polarization performance comparable to the polarizing film using iodine, and is excellent also in durability. Therefore, it is suitable for various liquid crystal display bodies and liquid crystal projectors, in-vehicle applications that require high polarization performance and durability, and display applications for industrial instruments used in various environments.
- the azo compound of the present invention is represented by the above formula (1).
- A represents a hydrogen atom, a hydroxy group, a C 1-5 alkoxy group having a sulfo group and / or a naphthyl group having a sulfo group, and at least one of R 1 to R 4 is a sulfo group.
- the other R 1 to R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- the compound of the formula (1) will be described. In the following substituents and the like, those having 1 to 4 carbon atoms are referred to as “lower”.
- the “substituent” includes a hydrogen atom, but will be described as a “substituent” for convenience.
- a which is the structure in the above formula (1) represents a naphthyl group having a substituent.
- the substituent is preferably a hydrogen atom, a sulfo group, a hydroxy group, a lower alkoxy group having a sulfo group, or a sulfo group. More preferably, A is a naphthyl group represented by the above formula (2), R 5 is a hydrogen atom, a hydroxy group, a C 1-5 alkoxy group having a sulfo group, or a sulfo group, and n is 1 to 3.
- the position of the sulfone group may be present in any benzene nucleus of the naphthalene ring.
- the lower alkoxy group having a sulfo group is preferably a linear alkoxy group, and the substitution position of the sulfo group is preferably an alkoxy group terminal. More preferred are a 3-sulfopropoxy group and a 4-sulfobutoxy group.
- the substitution position of the substituent that the naphthyl group has is not particularly limited. The number shown in the following formula (4) will be described.
- R 1 to R 4 may have a substituent, and the substituent is not limited.
- R 1 to R 4 each independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, more preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and particularly preferably , A lower alkoxy group having a hydrogen atom, a methyl group, an ethyl group or a sulfo group.
- the lower alkoxy group having a sulfo group in the above formula (1) is preferably a straight-chain alkoxy having 2 to 4 carbon atoms, and the substitution position of the sulfo group is the end of the alkoxy group. More preferred are a 3-sulfopropoxy group having 3 carbon atoms and a 4-sulfobutoxy group having 4 carbon atoms. Particularly preferred is a 3-sulfopropoxy group having 3 carbon atoms.
- the substitution position of R 1 to R 4 in the benzene ring is not particularly limited.
- the 2-position only the 5-position preferably only the 2-position, only the 5-position, a combination of the 2-position and the 6-position, a combination of the 2-position and the 5-position, and the 3-position and 5 -A combination of positions. More preferred are only the 2-position, only the 5-position, and combinations of the 2-position and the 5-position.
- the 2-position only and 5-position only indicate that only one substituent other than a hydrogen atom is present at the 2-position or 5-position only. Particularly preferred is a combination of a 3-sulfopropoxy group at the 2-position and other substituents at the 5-position.
- the azo compound represented by the above formula (1) or a salt thereof is prepared by diazotization, coupling, and ureido as described in Patent Document 3 in accordance with a conventional method for producing an azo dye as described in Non-Patent Document 1. It can be easily manufactured by performing the process. A specific manufacturing method is shown below.
- the aminonaphthalene (naphthylamine) having a substituent as shown by the following formula (i) is diazotized by the same production method as in Non-Patent Document 1, and coupled with anilines of the following formula (ii), and the following formula ( A monoazoamino compound represented by iii) is obtained.
- the monoazoamino compound (iii) is diazotized and secondarily coupled with anilines of the following formula (iv) to obtain a disazoamino compound represented by the following formula (v).
- the disazoamino compound (v) is reacted with phenyl chloroformate to obtain the azo compound of the above formula (1).
- the diazotization step is performed by a conventional method of mixing a nitrite such as sodium nitrite in a mineral acid aqueous solution or suspension of diazo component such as hydrochloric acid or sulfuric acid, or a neutral or weak alkaline solution of diazo component. Nitrite is added to the aqueous solution and mixed with mineral acid.
- the diazotization temperature is suitably -10 to 40 ° C.
- the coupling step with anilines is carried out by mixing an acidic aqueous solution such as hydrochloric acid or acetic acid with each of the above diazo solutions, and at a temperature of ⁇ 10 to 40 ° C. and acidic conditions of pH 2 to 7.
- the monoazoamino compound and disazoamino compound obtained by the coupling can be taken out as they are, or precipitated by aciding out or salting out and filtered, or can be used as a solution or suspension to proceed to the next step. If the diazonium salt is insoluble and in suspension, it can be filtered and used as a press cake in the next coupling step.
- phenols are disclosed on page 35 of Patent Document 4.
- a sulfoalkoxyaniline can be obtained by sulfoalkylation and reduction by the production method shown in the following, and can be used in the coupling step.
- a specific method for the ureido reaction between a disazoamino compound and phenyl chloroformate is carried out under neutral to alkaline conditions at a temperature of 10 to 90 ° C. and a pH of 7 to 11 according to the production method shown on page 57 of Patent Document 3. Is called. After completion of the reaction, it is precipitated by salting out and filtered out. If purification is required, salting out may be repeated or precipitated from water using an organic solvent.
- the organic solvent used for purification include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
- the azo compound represented by the above formula (1) can be used as a free acid or a salt of an azo compound.
- salts include organic salts such as alkali metal salts such as lithium salts, sodium salts, and potassium salts, ammonium salts, and amine salts. In general, a sodium salt is used.
- One of the starting materials for synthesizing the water-soluble dye represented by the formula (1) is a hydrogen atom, a hydroxy group, a C 1-4 alkoxy group having a sulfo group, or a naphthylamine having a sulfo group: A-NH 2 .
- Naphtylamines having a hydrogen atom, a hydroxyl group, and a sulfo group examples include 4-aminonaphthalenesulfonic acid, 7-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, 1- Aminonaphthalene-7-sulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,5-disulfonic acid, 7-aminonaphthalene-1 3,6-trisulfonic acid and the like.
- naphthylamines having a sulfo group and a C 1-5 alkoxy group having a sulfo group include, for example, 7-amino-3- (3-sulfopropoxy ) Naphthalene-1-sulfonic acid, 7-amino-3- (4-sulfobutoxy) naphthalene-1-sulfonic acid, 7-amino-3- (5-sulfopentoxy) naphthalene-1-sulfonic acid, 7-amino -4- (3-sulfopropoxy) naphthalene-2-sulfonic acid, 7-amino-4- (4-sulfobutoxy) naphthalene-2-sulfonic acid, 7-amino-4- (5-sulfopentoxy) naphthalene 2-sulfonic acid, 6-amino-4- (3-sulfopropoxy) naphthalene 2-sulfonic acid, 6-amino-4- (3
- R 1 to R 4 in the primary and secondary coupling components may have a substituent, and the substituent is not particularly limited.
- R 1 to R 4 each independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, more preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and particularly preferably It is a lower alkoxy group having a hydrogen atom, a methyl group, an ethyl group, or a sulfo group.
- the substitution positions of R 1 to R 4 in anilines are not limited.
- anilines that are primary and / or secondary couplers include aniline, 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 3-methylaniline, 3-ethylaniline, 3- Propylaniline, 3-butylaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-propoxyaniline, 2-butoxyaniline, 3-methoxyaniline, 3-ethoxy Aniline, 3-propoxyaniline, 3-butoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5-dimethylaniline, 2,6-dimethylaniline, 3,5-dimethoxyaniline, etc.
- anilines that are primary and / or secondary couplers include 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, 3- (2-aminophenoxy) propane-1-sulfone Acid, 4- (2-amino-4-methylphenoxy) butane-1-sulfonic acid, 4- (2-aminophenoxy) butane-1-sulfonic acid, 2- (2-amino-4-methylphenoxy) ethane 1-sulfonic acid, 2- (2-aminophenoxy) ethane-1-sulfonic acid, 3- (3-amino-4-methylphenoxy) propane-1-sulfonic acid, 3- (3-aminophenoxy) propane-1 -Sulfonic acid, 4- (3-amino-4-methylphenoxy) butane-1-sulfonic acid, 4- (3-aminophenoxy) butane-1-sulfonic acid, 2- (3-amino- -Methylphenoxy) ethane-1-sulf
- the azo compound represented by the above formula (1) or a salt thereof is used singly or in combination, and other organic dyes as necessary. May be used in combination.
- the organic dye to be combined is not particularly limited, but is preferably a dye having absorption characteristics in a wavelength region different from the absorption wavelength region of the azo compound or a salt thereof of the present invention and having high dichroism. For example, Sea. Ai. direct. Yellow 12, sea. Ai. direct. Yellow 28, Sea. Ai. direct. Yellow 44, Sea. Ai. direct. Orange 26, Sea. Ai. direct. Orange 39, sea. Ai. direct. Orange 71, Sea. Ai. direct. Orange 107, sea.
- Ai. direct. Red 2 sea. Ai. direct. Red 31, sea. Ai. direct. Red 79, Sea. Ai. direct. Red 81, Sea. Ai. direct. Red 247, Sea. Ai. direct. Blue 237, Sea. Ai. direct. Blue 273, Sea. Ai. direct. Blue 274, Sea. Ai. direct. Green 80, Sea. Ai. direct.
- Typical examples include Green 59 and dyes described in Patent Documents 1 to 5, but dyes developed for polarizing plates as described in Patent Documents 1 to 5 may be used depending on the purpose. More preferred. These dyes are used as free acids or alkali metal salts (for example, Na salt, K salt, Li salt), ammonium salts, and salts of amines.
- the type of dye to be blended differs depending on whether the target polarizing film is a neutral color polarizing film, a color polarizing film for liquid crystal projectors, or other color polarizing films.
- the blending ratio is not particularly limited, but in general, based on the mass of the azo compound of the above formula (1) or a salt thereof, a total of at least one of the above organic dyes is 0.1 to It is preferable to use in the range of 10 parts by mass.
- the azo compound represented by the above formula (1) or a salt thereof is contained in a polarizing film substrate (for example, a polymer film) and aligned with a known method together with other dyes, if necessary, and mixed with a liquid crystal.
- a polarizing film substrate for example, a polymer film
- polarizing films having various colors or neutral colors can be produced by orienting by a coating method.
- the obtained polarizing plate is provided with a protective film, and as a polarizing plate, a protective layer or an AR (antireflection) layer and a support are provided as necessary.
- the polarizing film substrate (polymer film) used in the dye-based polarizing film of the present invention is preferably a film made of polyvinyl alcohol resin or a derivative thereof. Specific examples thereof include polyvinyl alcohol or a derivative thereof, and any one of these. And those modified with olefins such as propylene and unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid and maleic acid.
- the film which consists of polyvinyl alcohol or its derivative (s) is used suitably from the point of the adsorptivity and orientation of a dye.
- the thickness of the substrate is usually about 30 to 100 ⁇ m, preferably about 50 to 80 ⁇ m.
- a method of dyeing a polymer film is usually employed.
- the staining is performed as follows.
- a dye bath is prepared by dissolving the azo compound of the present invention or a salt thereof and, if necessary, other dyes in water.
- the dye concentration in the dye bath is not particularly limited, but is usually selected from the range of about 0.001 to 10% by mass.
- a dyeing assistant may be used.
- Dyeing is performed by immersing the polymer film in the dyeing bath thus prepared for 1 to 10 minutes.
- the dyeing temperature is preferably about 40 to 80 ° C.
- Orientation of the azo compound of the above formula (1) or a salt thereof is performed by stretching the polymer film dyed as described above.
- a stretching method any known method such as a wet method or a dry method may be used.
- the stretching of the polymer film may optionally be performed before dyeing.
- the water-soluble dye is oriented at the time of dyeing.
- the polymer film containing and orienting the water-soluble dye is subjected to post-treatment such as boric acid treatment by a known method as necessary. Such post-processing is performed for the purpose of improving the light transmittance and the degree of polarization of the polarizing film.
- the conditions for the boric acid treatment vary depending on the type of polymer film used and the type of dye used, but generally the boric acid concentration of the boric acid aqueous solution is 0.1 to 15% by mass, preferably 1 to 10% by mass.
- the treatment is carried out by immersing in a temperature range of 30 to 80 ° C., preferably 40 to 75 ° C. for 0.5 to 10 minutes. Further, if necessary, the fixing treatment may be performed together with an aqueous solution containing a cationic polymer compound.
- the thus obtained dye-based polarizing film of the present invention can be made into a polarizing plate by laminating a transparent protective film excellent in optical transparency and mechanical strength on one side or both sides thereof.
- a transparent protective film excellent in optical transparency and mechanical strength on one side or both sides thereof.
- a material for forming the protective film for example, in addition to a cellulose acetate film and an acrylic film, a fluorine film such as a tetrafluoroethylene / hexafluoropropylene copolymer, a polyester resin, a polyolefin resin, or a polyamide film A resin film or the like is used.
- a triacetyl cellulose (TAC) film or a cycloolefin film is preferably used.
- the thickness of the protective film is usually 40 to 200 ⁇ m.
- Examples of adhesives that can be used to bond the polarizing film and the protective film include polyvinyl alcohol adhesives, urethane emulsion adhesives, acrylic adhesives, polyester-isocyanate adhesives, etc., and polyvinyl alcohol adhesives. Is preferred.
- a transparent protective layer may be further provided on the surface of the dye-based polarizing plate of the present invention.
- the protective layer include acrylic and polysiloxane hard coat layers and urethane protective layers.
- an AR layer on the protective layer.
- the AR layer can be formed by vapor deposition or sputtering treatment of a material such as silicon dioxide or titanium oxide, and can be formed by thinly applying a fluorine-based material.
- the dye-type polarizing plate of this invention can also be used as an elliptically polarizing plate which stuck the phase difference plate.
- the dye-based polarizing plate of the present invention configured in this way has a neutral color, has no color shift at an orthogonal position in the wavelength region of the visible light region, is excellent in polarization performance, and further can be discolored even at high temperature and high humidity.
- the polarization performance is not deteriorated, and the light leaks in the orthogonal position in the visible light region is small.
- the neutral gray polarizing plate for on-vehicle use in the present invention contains an azo compound represented by the above formula (1) or a salt thereof as a dichroic dye together with the other organic dyes as necessary. is there.
- the polarizing film used for the color polarizing plate for liquid crystal projectors of this invention is also manufactured by the said manufacturing method. These are further provided with a protective film as a polarizing plate, provided with a protective layer or an AR layer and a support as necessary, and used as a neutral gray polarizing plate for in-vehicle use.
- a necessary wavelength range of the polarizing plate (A. When an ultra-high pressure mercury lamp is used; 420 to 500 nm for a blue channel, 500 to 580 nm for a green channel, 600 to 680 nm for a red channel, B.3 Peak wavelength when using primary color LED lamps: blue channel 430 to 450 nm, green channel 520 to 535 nm, red channel 620 to 635 nm) average single plate light transmittance of 39% or more, average light transmittance at orthogonal position Is 0.4% or less, more preferably the single plate average light transmittance in the necessary wavelength region of the polarizing plate is 41% or more, and the average light transmittance in the orthogonal position is 0.3% or less, more preferably 0.2%.
- the single plate average light transmittance in the necessary wavelength region of the polarizing plate is 42% or more, and the average light transmittance in the orthogonal position is 0.1% or less.
- the color polarizing plate for a liquid crystal projector of the present invention has brightness and excellent polarization performance as described above.
- the single plate average light transmittance is that natural light is incident on a single polarizing plate (hereinafter simply referred to as a polarizing plate) having no support such as an AR layer and a transparent glass plate. It is the average value of the light transmittance in the specific wavelength region.
- the average light transmittance in the orthogonal position is an average value of the light transmittance in a specific wavelength region when natural light is incident on two polarizing plates whose orientation directions are orthogonal.
- the neutral gray polarizing plate for on-vehicle use of the present invention is preferably a polarizing plate comprising a polarizing film and a protective film, provided with the AR layer, and is preferably a polarizing plate with an AR layer, and is further attached to a support such as a transparent resin.
- a support such as a transparent resin.
- An AR layer and a polarizing plate with a support are more preferred.
- the neutral gray polarizing plate for on-vehicle use of the present invention is usually used as a polarizing plate with a support.
- the support preferably has a flat portion for attaching a polarizing plate, and a transparent substrate is preferable for optical use.
- Transparent substrates can be broadly divided into inorganic substrates and organic substrates. Inorganic substrates such as soda glass, borosilicate glass, quartz substrate, sapphire substrate, spinel substrate, acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, cycloolefin Although organic substrates, such as a polymer, are mentioned, an organic substrate is preferable.
- the thickness and size of the transparent substrate may be a desired size.
- the polarizing plate with a transparent substrate is preferably provided with an AR layer on one or both of the support surface and the polarizing plate surface.
- a transparent adhesive (adhesive) agent may be applied to the flat surface of the support, and then the dye-based polarizing plate of the present invention may be attached to the coated surface.
- a transparent adhesive (adhesive) agent may be applied to the polarizing plate, and then a support may be attached to the coated surface.
- the adhesive (adhesive) agent used here is preferably, for example, an acrylic ester-based one.
- the dye-based polarizing plate of the present invention is disposed on one or both of the incident side and the emission side of the liquid crystal cell.
- the polarizing plate may or may not be in contact with the liquid crystal cell, but is preferably not in contact from the viewpoint of durability.
- the dye-based polarizing plate of the present invention using the liquid crystal cell as a support can be used.
- the polarizing plate is not in contact with the liquid crystal cell, it is preferable to use the dye-based polarizing plate of the present invention using a support other than the liquid crystal cell.
- the dye-based polarizing plate of the present invention is disposed on either the incident side or the exit side of the liquid crystal cell, and the polarizing plate surface of the dye-based polarizing plate of the present invention is liquid crystal. It is preferable to arrange the support surface on the light source side on the cell side.
- the incident side of the liquid crystal cell is the light source side, and the opposite side is referred to as the emission side.
- the liquid crystal cell to be used is, for example, an active matrix type, between a transparent substrate on which an electrode and a TFT are formed and a transparent substrate on which a counter electrode is formed.
- the liquid crystal is preferably formed by encapsulating liquid crystal. Light emitted from a light source such as a cold-cathode tube lamp or a white LED passes through a neutral gray polarizing plate, and then passes through a liquid crystal cell, a color filter, and further a neutral gray polarizing plate and is projected onto a display screen.
- the neutral gray polarizing plate for in-vehicle use thus configured has excellent polarization performance, and further has the characteristics that it does not cause discoloration or decrease in polarization performance even in high temperature and high humidity conditions in the company.
- Example 1 30.3 parts of 7-aminonaphthalene-1,3-disulfonic acid is added to 400 parts of water and dissolved with sodium hydroxide. Add 10.4 parts of 35% hydrochloric acid, then add 6.9 parts of sodium nitrite and stir for 1 hour. Thereto was added 24.5 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid dissolved in water, and while stirring at 30 to 40 ° C., sodium carbonate was added to adjust the pH to 5, followed by further stirring. Thus, the coupling reaction was completed to obtain 50.4 parts of a monoazoamino compound represented by the following formula (30).
- Example 2 In the same manner as in Example 1 except that 7-aminonaphthalene-1,3-disulfonic acid is changed to 30.3 parts of 6-aminonaphthalene-1,3-disulfonic acid in Example 1, it is represented by the above formula (7). 41.4 parts of an azo compound of the invention was obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 480 nm.
- Example 3 In the same manner as in Example 1 except that 7-aminonaphthalene-1,3-disulfonic acid is changed to 30.3 parts of 7-aminonaphthalene-1,5-disulfonic acid in Example 1, the above formula (8) is shown. 41.4 parts of an azo compound of the invention was obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 523 nm.
- Example 4 In the same manner as in Example 1 except that 7-aminonaphthalene-1,3-disulfonic acid is changed to 22.3 parts of 6-aminonaphthalene-2-sulfonic acid in Example 1, 41.4 parts of the inventive azo compound were obtained.
- the maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 466 nm.
- Example 5 In the same manner as in the primary coupling of Example 1, 50.4 parts of the monoazoamino compound represented by the above formula (79) were obtained.
- Example 6 In the same manner as in Example 5 except that 2,5-dimethylaniline was changed to 9.8 parts of 2-methoxyaniline in Example 5, 35.3 parts of the azo compound of the present invention represented by the above formula (31) were obtained. It was. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 480 nm.
- Example 7 In Example 5, except that 7-aminonaphthalene-1,3-disulfonic acid was changed to 30.3 parts of 6-aminonaphthalene-1,3-disulfonic acid and 2,5-dimethylaniline was changed to 3-methylaniline. In the same manner as in Example 5, 34.5 parts of the azo compound of the present invention represented by the above formula (32) was obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 452 nm.
- Example 8 Add 30.3 parts of 7-aminonaphthalene-1,3-disulfonic acid to 400 parts of water and dissolve with sodium hydroxide. Add 10.4 parts of 35% hydrochloric acid, then add 6.9 parts of sodium nitrite and stir for 1 hour. Thereto was added 12.1 parts of 2,5-dimethylaniline, and while stirring at 30 to 40 ° C., sodium carbonate was added to adjust the pH to 5, and further stirred to complete the coupling reaction, which was represented by the following formula (82). 39.2 parts of a monoazoamino compound was obtained.
- Example 9 In Example 8, except that 7-aminonaphthalene-1,3-disulfonic acid was changed to 6-amino-4- (3-sulfopropoxy) naphthalene-2-sulfonic acid, the above formula (53 35.3 parts of the azo compound of the present invention represented by The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 480 nm.
- Example 10 In the same manner as in Example 8 except that 2,5-dimethylaniline was changed to 2-methoxyaniline in Example 8, 35.3 parts of the azo compound of the present invention represented by the above formula (54) were obtained.
- the maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 486 nm.
- Example 11 In the same manner as in Example 8 except that 7-aminonaphthalene-1,3-disulfonic acid is changed to 7-aminonaphthalene-1,5-disulfonic acid in Example 8, the present invention represented by the above formula (55) is used. 35.7 parts of azo compound were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 452 nm.
- Example 12 In the same manner as in Example 8 except that 2,5-dimethylaniline was changed to 2,5-dimethoxyaniline in Example 8, 36.8 parts of the azo compound of the present invention represented by the above formula (56) were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 510 nm.
- Example 13 In the same manner as in Example 8 except that 7-aminonaphthalene-1,3-disulfonic acid is changed to 6-aminonaphthalene-1,3-disulfonic acid in Example 8, the present invention represented by the above formula (57) is used. 35.2 parts of an azo compound were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 453 nm.
- Example 14 In the same manner as in Example 8 except that 2,5-dimethylaniline is changed to 2-methoxy-5-methylaniline in Example 8, 36.8 parts of the azo compound of the present invention represented by the above formula (58) are obtained. It was. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 487 nm.
- Example 15 Polyvinyl alcohol having a thickness of 75 ⁇ m was immersed in an aqueous solution at 45 ° C. having a concentration of 0.03% of the compound of the above formula (6) obtained in Example 1 and 0.1% of sodium sulfate for 4 minutes. This film was stretched 5 times in a 3% boric acid aqueous solution at 50 ° C., washed with water and dried while maintaining the tension state to obtain the polarizing film of the present invention. The obtained polarizing film had a maximum absorption wavelength of 526 nm, a polarization rate of 99.9%, and had a high polarization rate.
- Example 16 Polyvinyl alcohol having a thickness of 75 ⁇ m was immersed in an aqueous solution at 45 ° C. having a concentration of 0.03% of the compound of the above formula (30) obtained in Example 5 and 0.1% of sodium sulfate for 4 minutes. This film was stretched 5 times in a 3% boric acid aqueous solution at 50 ° C., washed with water and dried while maintaining the tension state to obtain the polarizing film of the present invention. The obtained polarizing film had a maximum absorption wavelength of 494 nm, a polarization rate of 99.9%, and had a high polarization rate.
- Example 17 Polyvinyl alcohol having a thickness of 75 ⁇ m was immersed in an aqueous solution at 45 ° C. having a concentration of 0.03% of the compound of the formula (52) obtained in Example 8 and 0.1% of sodium sulfate for 4 minutes. This film was stretched 5 times in a 3% boric acid aqueous solution at 50 ° C., washed with water and dried while maintaining the tension state to obtain the polarizing film of the present invention. The obtained polarizing film had a maximum absorption wavelength of 502 nm, a polarization rate of 99.9%, and had a high polarization rate.
- the measurement of the maximum absorption wavelength of the polarizing film and the calculation of the polarization rate were carried out by measuring the parallel transmittance and orthogonal transmittance at the time of polarized light incidence using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).
- the parallel transmittance (Ky) is the transmittance when the absorption axis of the absolute polarizer and the absorption axis of the polarizing film are parallel
- the orthogonal transmittance (Kz) is the absorption axis of the absolute polarizer and the polarizing film.
- the transmittance when the absorption axis is orthogonal is shown.
- the parallel transmittance and orthogonal transmittance at each wavelength were measured at 1 nm intervals at 380 to 780 nm.
- the polarization rate of each wavelength was calculated from the following formula (i) to obtain the highest polarization rate and its maximum absorption wavelength (nm) at 380 to 780 nm.
- Polarization rate (%) [(Ky ⁇ Kz) / (Ky + Kz)] ⁇ 100 (i)
- Example 18 to 20 The polarizing film of the present invention is used in the same manner as in Example 15 except that the azo compounds described in Examples 2 to 4 (compounds of the above formulas (7) to (9)) are used instead of the compound of the above formula (6).
- Table 1 shows the maximum absorption wavelength and polarization rate of the obtained polarizing film. As shown in Table 1, all the polarizing films prepared using these compounds had a high polarization rate.
- Example 21 and 22 The polarizing film of the present invention was obtained in the same manner as in Example 16 using the azo compound described in Examples 6 and 7 (compounds in the above formulas (31) and (32)) instead of the above formula (30). It was. Table 1 shows the maximum absorption wavelength and polarization rate of the obtained polarizing film. As shown in Table 1, all the polarizing films prepared using these compounds had a high polarization rate.
- Examples 23 to 28 The polarizing film of the present invention was used in the same manner as in Example 17 except that the azo compounds described in Examples 9 to 14 (compounds of the above formulas (53) to (58)) were used instead of the compound of the above formula (52). Got.
- Table 1 shows the maximum absorption wavelength and polarization rate of the obtained polarizing film. As shown in Table 1, all the polarizing films prepared using these compounds had a high polarization rate.
- One index representing the image quality is the contrast indicating the difference in luminance between white display and black display, which was obtained in Examples 15 and 18 to 20; 16, 21 and 22; and 17 and 23 to 28.
- Table 2 shows the maximum absorption wavelength of the polarizing film and the contrast at that time.
- the polarization performance was evaluated by making samples so that the parallel transmittances at the maximum absorption wavelength of the polarizing film were equal. As shown in Table 2, all the polarizing films prepared using these compounds had high contrast.
- Example 1 a polarizing film similar to Example 15 of the present invention was prepared by using the compound (4) in Patent Document 4 synthesized in the same manner as the method described in Example 2 of Patent Document 4. And the contrast was calculated. As shown in Table 2, all of the compounds of the present invention exhibited high contrast with respect to Comparative Example 1 and were excellent in polarization performance.
- Example 29 Compound (6) obtained in Example 1 was 0.2% of dye, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and 0.1% mirabilite.
- a polarizing film was prepared in the same manner as in Example 15 except that a 45 ° C. aqueous solution having a concentration of% was used.
- the maximum absorption wavelength of the obtained polarizing film was 576 nm, the single plate average transmittance at 380 to 600 nm was 42%, the average light transmittance at orthogonal positions was 0.02%, and had a high degree of polarization. .
- TAC film triacetyl cellulose film
- TD-80U triacetyl cellulose film
- An inventive dye-based polarizing plate neutral gray polarizing plate
- the polarizing plate of the present invention has a high polarization rate, and exhibited durability over a long period of time even in a high temperature and high humidity state. It also had excellent light resistance against long-term exposure.
- Example 30 The compound (30) obtained in Example 5 was 0.2% of dye, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and 0.1% mirabilite.
- a polarizing film was prepared in the same manner as in Example 16 except that a 45 ° C. aqueous solution having a concentration of% was used.
- the maximum absorption wavelength of the obtained polarizing film was 577 nm, the single plate average transmittance at 380 to 600 nm was 42%, the average light transmittance at orthogonal positions was 0.02%, and had a high degree of polarization. .
- TAC film triacetyl cellulose film
- TD-80U triacetyl cellulose film
- An inventive dye-based polarizing plate neutral gray polarizing plate
- the polarizing plate of the present invention has a high polarization rate, and exhibited durability over a long period of time even in a high temperature and high humidity state. It also had excellent light resistance against long-term exposure.
- Example 31 Compound (52) obtained in Example 8 was 0.2% of dye, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and 0.1% mirabilite.
- a polarizing film was prepared in the same manner as in Example 17 except that a 45 ° C. aqueous solution having a concentration of% was used.
- the maximum absorption wavelength of the obtained polarizing film was 575 nm, the single plate average transmittance at 380 to 600 nm was 42%, the average light transmittance at orthogonal positions was 0.02%, and had a high degree of polarization. .
- TAC film triacetyl cellulose film
- TD-80U triacetyl cellulose film
- An inventive dye-based polarizing plate neutral gray polarizing plate
- the polarizing plate of the present invention has a high polarization rate, and exhibited durability over a long period of time even in a high temperature and high humidity state. It also had excellent light resistance against long-term exposure.
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Abstract
Description
さらなる目的は車載液晶ディスプレイ用の染料系ニュートラルグレー偏光板であり、明るさと偏光性能、耐久性及び耐光性のいずれもが良好である高性能な偏光板を提供することにある。
下記式(1)
(式中、Aは水素原子、ヒドロキシ基、スルホ基を有する炭素数1~5のアルコキシ基及び/又はスルホ基を有するナフチル基であり、R1~R4の少なくとも1つは各々独立にスルホ基を有する炭素数1~4のアルコキシ基であり、他のR1~R4は各々独立に、水素原子、炭素数1~4のアルキル基又は炭素数1~4のアルコキシ基である)
で示されるアゾ化合物又はその塩、
<2>
上記式(1)において、前記他のR1~R4は各々独立に、水素原子、メチル基又はメトキシ基である、<1>に記載のアゾ化合物又はその塩、
<3>
(a)R1がスルホ基を有する炭素数1~4のアルコキシ基である、(b)R3がスルホ基を有する炭素数1~4のアルコキシ基である、又は(c)R1及びR3が各々独立にスルホ基を有する炭素数1~4のアルコキシ基である、<1>又は<2>に記載のアゾ化合物又はその塩、
<4>
上記式(1)において、スルホ基を有する低級アルコキシ基が3-スルホプロポキシ基である、<1>~<3>に記載のアゾ化合物又はその塩、
<5>
Aが下記式(2)
(式中、R5は水素原子、ヒドロキシ基、スルホ基を有する炭素数1~5のアルコキシ基、又はスルホ基であり、nは1~3の整数である)
で示される、<1>~<4>のいずれか一項に記載のアゾ化合物又はその塩、
<6>
下記式(3)
(R6は水素原子、ヒドロキシ基、及び/又はスルホ基を有する炭素数1~5のアルコキシ基であり、R7~R10の少なくとも1つはスルホ基を有する炭素数1~4のアルコキシ基であり、他のR7~R10は各々独立に、水素原子、炭素数1~4のアルキル基又は炭素数1~4のアルコキシ基であり、xは1~3の整数である)
で示されるアゾ化合物又はその塩、
<7>
上記式(3)において、スルホ基を有する炭素数1~4のアルコキシ基ではないR7~R10が各々独立して、水素原子、メチル基、メトキシ基である、<6>に記載のアゾ化合物又はその塩、
<8>
(a)R8がスルホ基を有する炭素数1~4のアルコキシ基である、(b)R10がスルホ基を有する炭素数1~4のアルコキシ基である、又は(c)R8及びR10が各々独立にスルホ基を有する炭素数1~4のアルコキシ基である、<6>又は<7>に記載のアゾ化合物又はその塩、
<9>
上記式(3)において、R6が水素原子であり、xが2である、<6>~<8>のいずれか一項に記載のアゾ化合物又はその塩、
<10>
上記式(3)において、スルホ基を有する炭素数1~4のアルコキシ基が3-スルホプロポキシ基である、<6>~<9>のいずれか一項に記載のアゾ化合物又はその塩、
<11>
<1>~<10>のいずれか一項に記載のアゾ化合物又はその塩を含有する偏光膜基材を含む、染料系偏光膜、
<12>
<1>~<10>のいずれか一項に記載のアゾ化合物又はその塩、並びにこれら以外の有機染料を1種類以上含有する偏光膜基材を含む、染料系偏光膜、
<13>
偏光膜基材がポリビニルアルコール樹脂又はその誘導体からなるフィルムである、<11>又は<12>に記載の染料系偏光膜、
<14>
<11>~<13>のいずれか一項に記載の染料系偏光膜の少なくとも一方の面に透明保護層を貼合して得られうる、染料系偏光板、
<15>
<11>~<13>のいずれか一項に記載の染料系偏光膜又は<14>に記載の染料系偏光板を用いる、液晶表示用偏光板、
<16>
<11>~<13>のいずれか一項に記載の染料系偏光膜、<14>に記載の染料系偏光板、又は<15>に記載の液晶表示用偏光板を用いる、車載用途用ニュートラルグレー偏光板、
<17>
<14>に記載の染料系偏光板、<15>に記載の液晶表示用偏光板、又は<16>に記載の車載用途用ニュートラルグレー偏光板を用いる、液晶表示装置、
に関する。
以下、式(1)の化合物について説明するが、以下の置換基等において、炭素数1~4は「低級」と称す。
また、本願において、「置換基」は水素原子を含むが、便宜上「置換基」として説明する。
上記式(1)中の構造であるAは置換基を有するナフチル基を示す。その置換基としては水素原子、スルホ基、ヒドロキシ基、スルホ基を有する低級アルコキシ基、スルホ基が好ましい。より好ましくは、Aは上記式(2)に示すナフチル基であり、R5は水素原子、ヒドロキシ基、スルホ基を有する炭素数1~5のアルコキシ基、又はスルホ基を示し、nは1~3である。また、スルホン基の位置はナフタレン環のどちらのベンゼン核に有していてもよい。スルホ基を有する低級アルコキシ基としては、直鎖アルコキシ基が好ましく、スルホ基の置換位置はアルコキシ基末端が好ましい。より好ましくは3-スルホプロポキシ基、4-スルホブトキシ基である。ナフチル基が有する置換基の置換位置は特に限定されない。下記式(4)に示す番号で説明すると、置換基が2個の場合は5-位と7-位、又は6-位と8-位の組合せが好ましく、置換基が3個の場合は3-位と5-位と7-位、3-位と6-位と8-位が好ましい。
ベンゼン環におけるR1~R4の置換位置は特に限定されない。下記式(5)に示す番号で説明すると、好ましくは、2-位のみ、5-位のみ、2-位と6-位の組合せ、2-位と5-位の組合せ、3-位と5-位の組合せである。さらに好ましくは、2-位のみ、5-位のみ、2-位と5-位の組合せである。なお、前記において、2-位のみ、5-位のみとは、2-位または5-位のみに水素原子以外の置換基を1つ有することを示す。特に好ましくは、2-位に3-スルホプロポキシ基、5-位にそれ以外の置換基の組合せである。
具体的な製造方法を以下に示す。
下記式(i)で示されるような、置換基を有するアミノナフタレン(ナフチルアミン)類を非特許文献1と同様の製法によりジアゾ化し、下記式(ii)のアニリン類とカップリングさせ、下記式(iii)で示されるモノアゾアミノ化合物を得る。
アニリン類におけるR1~R4の置換位置は限定されない。好ましくは、2-位のみ、5-位のみ、2-位と6-位の組合せ、2-位と5-位の組合せ、3-位と5-位の組合せであり、特に好ましくは、2-位のみ、5-位のみ、2-位と5-位の組合せである。
一次及び/又は二次カップラであるアニリン類の例としては、アニリン、2-メチルアニリン、2-エチルアニリン、2-プロピルアニリン、2-ブチルアニリン、3-メチルアニリン、3-エチルアニリン、3-プロピルアニリン、3-ブチルアニリン、2,5-ジメチルアニリン、2,5-ジエチルアニリン、2-メトキシアニリン、2-エトキシアニリン、2-プロポキシアニリン、2-ブトキシアニリン、3-メトキシアニリン、3-エトキシアニリン、3-プロポキシアニリン、3-ブトキシアニリン、2-メトキシ-5-メチルアニリン、2,5-ジメトキシアニリン、3,5-ジメチルアニリン、2,6-ジメチルアニリン又は3,5-ジメトキシアニリン等が挙げられる。
一次及び/又は二次カップラであるアニリン類の他の例としては、3-(2-アミノ-4-メチルフェノキシ)プロパン-1-スルホン酸、3-(2-アミノフェノキシ)プロパン-1-スルホン酸、4-(2-アミノ-4-メチルフェノキシ)ブタン-1-スルホン酸、4-(2‐アミノフェノキシ)ブタン-1-スルホン酸、2-(2-アミノ-4-メチルフェノキシ)エタン―1-スルホン酸、2-(2-アミノフェノキシ)エタン-1-スルホン酸、3-(3-アミノ-4-メチルフェノキシ)プロパン-1-スルホン酸、3-(3-アミノフェノキシ)プロパン-1-スルホン酸、4-(3‐アミノ-4-メチルフェノキシ)ブタン-1-スルホン酸、4-(3-アミノフェノキシ)ブタン-1-スルホン酸、2-(3-アミノ-4-メチルフェノキシ)エタン-1-スルホン酸、2-(3-アミノフェノキシ)エタン-1-スルホン酸、3-(2-アミノ-4-メトキシフェノキシ)プロパン-1-スルホン酸、4-(2-アミノ-4-メトキシフェノキシ)ブタン-1-スルホン酸、-(2-アミノ-4-メトキシフェノキシ)エタン―1-スルホン酸 等、3-(3-アミノ-4-メトキシフェノキシ)プロパン-1-スルホン酸、4-(3-アミノ-4-メトキシフェノキシ)ブタン-1-スルホン酸、2-(3-アミノ-4-メトキシフェノキシ)エタン-1-スルホン酸、3-(2-アミノ-4-エトキシフェノキシ)プロパン-1-スルホン酸、4-(2-アミノ-4-エトキシフェノキシ)ブタン-1-スルホン酸、-(2-アミノ-4-エトキシフェノキシ)エタン―1-スルホン酸 等、3-(3-アミノ-4-エトキシフェノキシ)プロパン-1-スルホン酸、4-(3-アミノ-4-エトキシフェノキシ)ブタン-1-スルホン酸、2-(3-アミノ-4-エトキシフェノキシ)エタン-1-スルホン酸、等が挙げられる。好ましくは3-(2-アミノ-4-メチルフェノキシ)プロパン-1-スルホン酸、3-(2-アミノフェノキシ)プロパン-1-スルホン酸、4-(2-アミノ-4-メチルフェノキシ)ブタン-1-スルホン酸、4-(2‐アミノフェノキシ)ブタン-1-スルホン酸、2-(2-アミノ-4-メチルフェノキシ)エタン―1-スルホン酸、2-(2-アミノフェノキシ)エタン-1-スルホン酸、3-(3-アミノ-4-メチルフェノキシ)プロパン-1-スルホン酸、3-(3-アミノフェノキシ)プロパン-1-スルホン酸、4-(3‐アミノ-4-メチルフェノキシ)ブタン-1-スルホン酸、4-(3-アミノフェノキシ)ブタン-1-スルホン酸、2-(3-アミノ-4-メチルフェノキシ)エタン-1-スルホン酸、2-(3-アミノフェノキシ)エタン-1-スルホン酸、3-(2-アミノ-4-メトキシフェノキシ)プロパン-1-スルホン酸、4-(2-アミノ-4-メトキシフェノキシ)ブタン-1-スルホン酸、-(2-アミノ-4-メトキシフェノキシ)エタン―1-スルホン酸、3-(3-アミノ-4-メトキシフェノキシ)プロパン-1-スルホン酸、4-(3-アミノ-4-メトキシフェノキシ)ブタン-1-スルホン酸、2-(3-アミノ-4-メトキシフェノキシ)エタン-1-スルホン酸であり、特に好ましくは3-(2-アミノ-4-メチルフェノキシ)プロパン-1-スルホン酸、3-(2-アミノ-4-メチルフェノキシ)ブタン-1-スルホン酸である。
これらのアニリン類はアミノ基が保護されていてもよい。保護基としては、例えばそのω-メタンスルホン基が挙げられる。
偏光膜と保護膜を貼り合わせるのに用いうる接着剤としては、ポリビニルアルコール系接着剤、ウレタンエマルジョン系接着剤、アクリル系接着剤、ポリエステルーイソシアネート系接着剤などが挙げられ、ポリビニルアルコール系接着剤が好適である。
7-アミノナフタレン-1、3-ジスルホン酸30.3部を水400部に加え、水酸化ナトリウムで溶解する。35%塩酸10.4部を加え、次に亜硝酸ナトリウム6.9部を加え、1時間攪拌する。そこへ水に溶解した3-(2-アミノ-4-メチルフェノキシ)プロパン-1-スルホン酸24.5部を加え、30~40℃で攪拌しながら、炭酸ナトリウムを加えてpH5とし、さらに攪拌してカップリング反応を完結させ、下記式(30)で示されるモノアゾアミノ化合物を50.4部得た。
実施例1において7-アミノナフタレン-1、3-ジスルホン酸を6-アミノナフタレン-1、3-ジスルホン酸30.3部に変更する以外は実施例1と同様にして上記式(7)で示される本発明のアゾ化合物41.4部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は480nmであった。
実施例1において7-アミノナフタレン-1、3-ジスルホン酸を7-アミノナフタレン-1、5-ジスルホン酸30.3部に変更する以外は実施例1と同様にして上記式(8)で示される本発明のアゾ化合物41.4部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は523nmであった。
実施例1において7-アミノナフタレン-1、3-ジスルホン酸を6-アミノナフタレン-2-スルホン酸22.3部に変更する以外は実施例1と同様にして上記式(9)で示される本発明のアゾ化合物41.4部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は466nmであった。
上記実施例1の1次カップリングと同様にして上記式(79)で示されるモノアゾアミノ化合物を50.4部得た。
実施例5において2,5-ジメチルアニリンを2-メトキシアニリン9.8部に変更する以外は実施例5と同様にして上記式(31)で示される本発明のアゾ化合物35.3部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は480nmであった。
実施例5において7-アミノナフタレン-1,3-ジスルホン酸を6-アミノナフタレン-1、3-ジスルホン酸30.3部に、2,5-ジメチルアニリンを3-メチルアニリンに変更する以外は実施例5と同様にして上記式(32)で示される本発明のアゾ化合物34.5部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は452nmであった。
7-アミノナフタレン-1,3-ジスルホン酸30.3部を水400部に加え、水酸化ナトリウムで溶解する。35%塩酸10.4部を加え、次に亜硝酸ナトリウム6.9部を加え、1時間攪拌する。そこへ2,5-ジメチルアニリン12.1部を加え、30~40℃で攪拌しながら、炭酸ナトリウムを加えてpH5とし、さらに攪拌してカップリング反応を完結させ、下記式(82)で示されるモノアゾアミノ化合物を39.2部得た。
実施例8において7-アミノナフタレン-1,3-ジスルホン酸を6-アミノ-4-(3-スルホプロポキシ)ナフタレン-2-スルホン酸に変更する以外は実施例8と同様にして上記式(53)で示される本発明のアゾ化合物35.3部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は480nmであった。
実施例8において2,5-ジメチルアニリンを2-メトキシアニリンに変更する以外は実施例8と同様にして上記式(54)で示される本発明のアゾ化合物35.3部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は486nmであった。
実施例8において7-アミノナフタレン-1,3-ジスルホン酸を7-アミノナフタレン-1,5-ジスルホン酸に変更する以外は実施例8と同様にして上記式(55)で示される本発明のアゾ化合物35.7部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は452nmであった。
実施例8において2,5-ジメチルアニリンを2,5-ジメトキシアニリンに変更する以外は実施例8と同様にして上記式(56)で示される本発明のアゾ化合物36.8部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は510nmであった。
実施例8において7-アミノナフタレン-1,3-ジスルホン酸を6-アミノナフタレン-1,3-ジスルホン酸に変更する以外は実施例8と同様にして上記式(57)で示される本発明のアゾ化合物35.2部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は453nmであった。
実施例8において2,5-ジメチルアニリンを2-メトキシ-5-メチルアニリンに変更する以外は実施例8と同様にして上記式(58)で示される本発明のアゾ化合物36.8部を得た。この化合物の20%ピリジン水溶液中の極大吸収波長は487nmであった。
実施例1で得られた上記式(6)の化合物の0.03%および芒硝0.1%の濃度とした45℃の水溶液に、厚さ75μmのポリビニルアルコールを4分間浸漬した。このフィルムを3%ホウ酸水溶液中で、50℃で5倍に延伸し、緊張状態を保ったまま水洗、乾燥して本発明の偏光膜を得た。
得られた偏光膜の極大吸収波長は526nmであり、偏光率は99.9%であり、高い偏光率を有していた。
実施例5で得られた上記式(30)の化合物の0.03%および芒硝0.1%の濃度とした45℃の水溶液に、厚さ75μmのポリビニルアルコールを4分間浸漬した。このフィルムを3%ホウ酸水溶液中で、50℃で5倍に延伸し、緊張状態を保ったまま水洗、乾燥して本発明の偏光膜を得た。
得られた偏光膜の極大吸収波長は494nmであり、偏光率は99.9%であり、高い偏光率を有していた。
実施例8で得られた上記式(52)の化合物の0.03%および芒硝0.1%の濃度とした45℃の水溶液に、厚さ75μmのポリビニルアルコールを4分間浸漬した。このフィルムを3%ホウ酸水溶液中で、50℃で5倍に延伸し、緊張状態を保ったまま水洗、乾燥して本発明の偏光膜を得た。
得られた偏光膜の極大吸収波長は502nmであり、偏光率は99.9%であり、高い偏光率を有していた。
ここで平行透過率(Ky)とは、絶対偏光子の吸収軸と偏光膜の吸収軸が平行時の透過率であり、直交透過率(Kz)とは、絶対偏光子の吸収軸と偏光膜の吸収軸が直交時の透過率を示す。
各波長の平行透過率及び直交透過率は、380~780nmにおいて、1nm間隔で測定した。それぞれ測定した値を用いて、下記式(i)より各波長の偏光率を算出し、380乃至780nmにおいて最も高い時の偏光率と、その極大吸収波長(nm)を得た。
上記式(6)の化合物に代えて、実施例2~4に記載のアゾ化合物(上記式(7)~(9)の化合物)を用いて、実施例15と同様にして本発明の偏光膜を得た。得られた偏光膜の極大吸収波長及び偏光率を表1に示す。
表1の通り、これらの化合物を用いて作成した偏光膜は、いずれも高い偏光率を有していた。
上記式(30)に代えて、実施例6及び7に記載のアゾ化合物(上記式(31)及び(32)の化合物)を用いて、実施例16と同様にして本発明の偏光膜を得た。得られた偏光膜の極大吸収波長及び偏光率を表1に示す。
表1の通り、これらの化合物を用いて作成した偏光膜は、いずれも高い偏光率を有していた。
上記式(52)の化合物に代えて、実施例9~14に記載のアゾ化合物(上記式(53)~(58)の化合物)を用いて、実施例17と同様にして本発明の偏光膜を得た。得られた偏光膜の極大吸収波長及び偏光率を表1に示す。
表1の通り、これらの化合物を用いて作成した偏光膜は、いずれも高い偏光率を有していた。
画像の質を表す一つの指標として、白表示と黒表示での輝度の差を示すコントラストがあり、実施例15及び18~20;16、21及び22;並びに17及び23~28で得られた偏光膜の極大吸収波長及びその際のコントラストを表2に示す。ここでコントラストとは、平行透過率と直交透過率の比(コントラスト=極大吸収波長での平行透過率(Ky)/極大吸収波長での直行透過率(Kz))を示し、この値が大きいほど偏光板の偏光性能が優れているということを表す。なお、偏光性能の評価は、偏光膜の極大吸収波長の平行透過率が等しくなるようにサンプルを作成し、比較を行った。表2に示した通り、これらの化合物を用いて作成した偏光膜はいずれも高いコントラストを有していた。
本発明の化合物に代えて、特許文献4中の実施例2に記載された方法と同様に合成した特許文献4中の化合物(4)を用いて、本発明の実施例15と同様に偏光膜を作成し、コントラストを算出した。表2に示した通り、本発明の化合物は、比較例1に対しいずれも高いコントラストを示し、偏光性能に優れていた。
本発明の化合物に代えて、特許文献5中の[0077]に記載された方法と同様に合成した化合物(I-3)を用いて、本発明の実施例15と同様に偏光膜を作成し、コントラストを算出した。表2に示した通り、本発明の化合物は、比較例2に対しいずれも高いコントラストを示し、偏光性能に優れていた。
実施例1で得られた化合物(6)を染料0.2%、シー・アイ・ダイレクト・オレンジ39を0.07%、シー・アイ・ダイレクト・ブルー274を0.02%及び芒硝0.1%の濃度とした45℃の水溶液を用いる以外は実施例15と同様にして偏光膜を作成した。得られた偏光膜の極大吸収波長は576nmであり、380~600nmにおける単板平均透過率は42%、直交位の平均光透過率は0.02%であり、高い偏光度を有していた。
この偏光膜の両面にポリビニルアルコール水溶液の接着剤を介してトリアセチルセルロースフィルム(TACフィルム;富士写真フィルム社製;商品名TD-80U)をラミネートし、粘着剤を用いてAR支持体付きの本発明の染料系偏光板(ニュートラルグレー偏光板)を得た。本発明の偏光板は、高い偏光率を有し、かつ高温且つ高湿の状態でも長時間にわたる耐久性を示した。また長時間暴露に対する耐光性も優れていた。
実施例5で得られた化合物(30)を染料0.2%、シー・アイ・ダイレクト・オレンジ39を0.07%、シー・アイ・ダイレクト・ブルー274を0.02%及び芒硝0.1%の濃度とした45℃の水溶液を用いる以外は実施例16と同様にして偏光膜を作成した。得られた偏光膜の極大吸収波長は577nmであり、380~600nmにおける単板平均透過率は42%、直交位の平均光透過率は0.02%であり、高い偏光度を有していた。
この偏光膜の両面にポリビニルアルコール水溶液の接着剤を介してトリアセチルセルロースフィルム(TACフィルム;富士写真フィルム社製;商品名TD-80U)をラミネートし、粘着剤を用いてAR支持体付きの本発明の染料系偏光板(ニュートラルグレー偏光板)を得た。本発明の偏光板は、高い偏光率を有し、かつ高温且つ高湿の状態でも長時間にわたる耐久性を示した。また長時間暴露に対する耐光性も優れていた。
実施例8で得られた化合物(52)を染料0.2%、シー・アイ・ダイレクト・オレンジ39を0.07%、シー・アイ・ダイレクト・ブルー274を0.02%及び芒硝0.1%の濃度とした45℃の水溶液を用いる以外は実施例17と同様にして偏光膜を作成した。得られた偏光膜の極大吸収波長は575nmであり、380~600nmにおける単板平均透過率は42%、直交位の平均光透過率は0.02%であり、高い偏光度を有していた。
この偏光膜の両面にポリビニルアルコール水溶液の接着剤を介してトリアセチルセルロースフィルム(TACフィルム;富士写真フィルム社製;商品名TD-80U)をラミネートし、粘着剤を用いてAR支持体付きの本発明の染料系偏光板(ニュートラルグレー偏光板)を得た。本発明の偏光板は、高い偏光率を有し、かつ高温且つ高湿の状態でも長時間にわたる耐久性を示した。また長時間暴露に対する耐光性も優れていた。
Claims (17)
- 上記式(1)において、前記他のR1~R4は各々独立に、水素原子、メチル基又はメトキシ基である、請求項1に記載のアゾ化合物又はその塩、
- (a)R1がスルホ基を有する炭素数1~4のアルコキシ基である、(b)R3がスルホ基を有する炭素数1~4のアルコキシ基である、又は(c)R1及びR3が各々独立にスルホ基を有する炭素数1~4のアルコキシ基である、請求項1又は2に記載のアゾ化合物又はその塩、
- 上記式(1)において、スルホ基を有する低級アルコキシ基が3-スルホプロポキシ基である、請求項1~3に記載のアゾ化合物又はその塩、
- 上記式(3)において、スルホ基を有する炭素数1~4のアルコキシ基ではないR7~R10が各々独立して、水素原子、メチル基、メトキシ基である、請求項6に記載のアゾ化合物又はその塩、
- (a)R8がスルホ基を有する炭素数1~4のアルコキシ基である、(b)R10がスルホ基を有する炭素数1~4のアルコキシ基である、又は(c)R8及びR10が各々独立にスルホ基を有する炭素数1~4のアルコキシ基である、請求項6又は7に記載のアゾ化合物又はその塩、
- 上記式(3)において、R6が水素原子であり、xが2である、請求項6~8のいずれか一項に記載のアゾ化合物又はその塩、
- 上記式(3)において、スルホ基を有する炭素数1~4のアルコキシ基が3-スルホプロポキシ基である、請求項6~9のいずれか一項に記載のアゾ化合物又はその塩、
- 請求項1~10のいずれか一項に記載のアゾ化合物又はその塩を含有する偏光膜基材を含む、染料系偏光膜、
- 請求項1~10のいずれか一項に記載のアゾ化合物又はその塩、並びにこれら以外の有機染料を1種類以上含有する偏光膜基材を含む、染料系偏光膜、
- 偏光膜基材がポリビニルアルコール樹脂又はその誘導体からなるフィルムである、請求項11又は12に記載の染料系偏光膜、
- 請求項11~13のいずれか一項に記載の染料系偏光膜の少なくとも一方の面に透明保護層を貼合して得られうる、染料系偏光板、
- 請求項11~13のいずれか一項に記載の染料系偏光膜又は請求項14に記載の染料系偏光板を用いる、液晶表示用偏光板、
- 請求項11~13のいずれか一項に記載の染料系偏光膜、請求項14に記載の染料系偏光板、又は請求項15に記載の液晶表示用偏光板を用いる、車載用途用ニュートラルグレー偏光板、
- 請求項14に記載の染料系偏光板、請求項15に記載の液晶表示用偏光板、又は請求項16に記載の車載用途用ニュートラルグレー偏光板を用いる、液晶表示装置、
に関する。
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KR20200046016A (ko) | 2017-08-31 | 2020-05-06 | 미쯔비시 케미컬 주식회사 | 편광판, 액정표시장치 및 이의 제조 방법, 및 폴리비닐알코올계 편광 필름 |
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JP6736549B2 (ja) | 2020-08-05 |
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