WO2016186194A1 - 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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- WO2016186194A1 WO2016186194A1 PCT/JP2016/064986 JP2016064986W WO2016186194A1 WO 2016186194 A1 WO2016186194 A1 WO 2016186194A1 JP 2016064986 W JP2016064986 W JP 2016064986W WO 2016186194 A1 WO2016186194 A1 WO 2016186194A1
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- Prior art keywords
- group
- amino
- polarizing plate
- independently
- dye
- Prior art date
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- 0 CC1(CC2CC2)C=C(*=*C2=CC=C(**)C=I2)C=CC=C1 Chemical compound CC1(CC2CC2)C=C(*=*C2=CC=C(**)C=I2)C=CC=C1 0.000 description 5
- UIHDBJCTORGLQP-MSLYZBPISA-N Cc(cc(c(C)c1)/N=N/c(c(OCCCCS(O)(=O)=O)c2)cc(C)c2/N=N/c(cc2)c(C)cc2S(O)(=O)=O)c1NC(Nc(c(C)c1)cc(C)c1/N=N\c(cc(C)c(/N=N/c(cc1)c(C)cc1S(O)(=O)=O)c1)c1OCCCCS(O)(=O)=O)=O Chemical compound Cc(cc(c(C)c1)/N=N/c(c(OCCCCS(O)(=O)=O)c2)cc(C)c2/N=N/c(cc2)c(C)cc2S(O)(=O)=O)c1NC(Nc(c(C)c1)cc(C)c1/N=N\c(cc(C)c(/N=N/c(cc1)c(C)cc1S(O)(=O)=O)c1)c1OCCCCS(O)(=O)=O)=O UIHDBJCTORGLQP-MSLYZBPISA-N 0.000 description 1
- XJCVFBCLAGXWIS-SNQKRLHOSA-N Cc(cc(c(C)c1)/N=N/c(c(OCCCS(O)(=O)=O)c2)cc(C)c2/N=N\c(ccc(OCCCS(O)(=O)=O)c2)c2S(O)(=O)=O)c1N Chemical compound Cc(cc(c(C)c1)/N=N/c(c(OCCCS(O)(=O)=O)c2)cc(C)c2/N=N\c(ccc(OCCCS(O)(=O)=O)c2)c2S(O)(=O)=O)c1N XJCVFBCLAGXWIS-SNQKRLHOSA-N 0.000 description 1
- POMXTHQMMXYUQQ-QQQQZANTSA-N Cc1cc(/N=N\c(c(OCCCSO)c2)cc(C)c2/N=N\c(cc2)ccc2S(O)(=O)=O)c(C)cc1NC(Nc(c(C)c1)cc(C)c1/N=N/c(c(OCCCS(O)(=O)=O)c1)cc(C)c1/N=N/c(cc1)ccc1S(O)(=O)=O)=O Chemical compound Cc1cc(/N=N\c(c(OCCCSO)c2)cc(C)c2/N=N\c(cc2)ccc2S(O)(=O)=O)c(C)cc1NC(Nc(c(C)c1)cc(C)c1/N=N/c(c(OCCCS(O)(=O)=O)c1)cc(C)c1/N=N/c(cc1)ccc1S(O)(=O)=O)=O POMXTHQMMXYUQQ-QQQQZANTSA-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
-
- 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
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/30—Other polyazo dyes
-
- 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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- 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
-
- 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
- G02F1/133528—Polarisers
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.
- R 1 to R 6 is each independently a C 1-4 alkoxy group having a sulfo group
- the other R 1 and R 2 are each independently a hydrogen atom, a sulfo group, Group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, a nitro group, an amino group, an alkyl-substituted amino group having 1 to 4 carbon atoms, or an alkyl-substituted acylamino group having 1 to 4 carbon atoms
- the other R 3 to R 6 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 formula (1), R 1 to R 6 which are not alkoxy groups having 1 to 4 carbon atoms having a sulfo
- R 1 is a C 1-4 alkoxy group having a sulfo group
- R 3 is a C 1-4 alkoxy group having a sulfo group
- R 5 is a C 1-4 alkoxy group having a sulfo group
- R 1 and R 3 are each independently a C 1-4 alkoxy group having a sulfo group
- R 1 and R 5 are each independently a C 1-4 alkoxy group having a sulfo group
- R 3 and R 5 are each independently a C 1-4 alkoxy group having a sulfo group
- the azo compound or a 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).
- the compound of the formula (1) will be described.
- the “substituent” includes a hydrogen atom, but will be described as a “substituent” for convenience.
- at least one of R 1 to R 6 has a sulfo group and the alkoxy group having 1 to 4 carbon atoms preferably has 2 to 4 carbon atoms, more preferably 3 or 4 carbon atoms. , More preferably 3.
- the substitution position of the sulfo group is not particularly limited, but is preferably the terminal of the alkoxy group.
- Particularly preferred alkoxy groups having 1 to 4 carbon atoms having a sulfo group are a 3-sulfopropoxy group and a 4-sulfobutoxy group, and most preferably a 3-sulfopropoxy group.
- R 1 may be a C 1-4 alkoxy group having a sulfo group
- R 3 may be a C 1-4 alkoxy group having a sulfo group
- R 5 May be a C 1-4 alkoxy group having a sulfo group
- R 1 and R 3 may each independently be a C 1-4 alkoxy group having a sulfo group
- R 1 and R 3 5 may be an alkoxy group having 1 to 4 carbon atoms each independently having a sulfo group
- R 3 and R 5 may be each independently an alkoxy group having 1 to 4 carbon atoms having a sulfo group
- R 1 , R 3 and R 5 may each independently be an alkoxy group having 1 to 4 carbon atoms having a sulfo group.
- R 1 and R 2 may have a substituent, and the substituent is not particularly limited.
- the other R 1 and R 2 are each independently a hydrogen atom, a sulfo group, a carboxy group, a lower alkyl group, a lower alkoxy group, a lower alkoxy group having a sulfo group, a halogen group, a nitro group, an amino group, a lower group, An alkyl-substituted amino group, a lower alkyl-substituted acylamino group, or the like.
- R 1 and R 2 are not a hydrogen atom
- at least one of the other R 1 and R 2 is preferably a sulfo group or a carboxy group.
- the substitution positions of R 1 and R 2 in the benzene ring are not particularly limited, but preferably 2-position only, 4-position only, 2-position and 6-position combination, 2-position and 4-position combination, It is a combination of the 3-position and the 5-position, and more preferably, only the 2-position, only the 4-position, a combination of the 2-position and the 4-position, or a combination of the 3-position and the 5-position.
- the 2-position only and 4-position only indicate that only one substituent other than a hydrogen atom is present at the 2-position or 4-position only.
- the other substituents R 3 to R 6 are not particularly limited, but are preferably each independently selected from a hydrogen atom, a lower alkyl group, and a lower alkoxy group. More preferred are a hydrogen atom, methyl group, ethyl group, methoxy group, and ethoxy group, and particularly preferred are a hydrogen atom, methyl group, and methoxy group.
- substitution position of R 3 to R 6 in the benzene ring is not particularly limited, but preferably, the number shown in the formula (3) will explain the 2-position only, the 5-position only, and the combination of the 2-position and the 6-position , A combination of 2-position and 5-position, a combination of 3-position and 5-position, particularly preferably 2-position only, 5-position only, 2-position and 5-position combination, or 3- It is a combination of position and 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.
- 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.
- anilines having a substituent represented by the following formula (i) are diazotized by the same production method as in Non-Patent Document 1, and coupled with anilines of the following formula (ii), A monoazoamino compound represented by the following formula (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 azo compound of the above formula (1) is obtained by reacting this disazoamino compound (v) with phenyl chloroformate.
- 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 the solution or the suspension can be used for 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.
- sulfoalkoxyanilines are obtained by sulfoalkylating and reducing phenols by the production method shown on page 35 of Patent Document 4. Can be used in the coupling process.
- 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.
- substituents of anilines having an alkoxy group having a sulfo group which is one of the starting materials for synthesizing the water-soluble dye represented by the above formula (1), are a hydrogen atom, a sulfo group, a carboxy group, A lower alkyl group, a lower alkoxy group, a chloro group, a bromo group and a nitro group; More preferred are a hydrogen atom, a sulfo group, a carboxy group, a methyl group, and a methoxy group.
- the alkoxy group having 1 to 4 carbon atoms having a sulfo group is preferably a linear alkoxy group having 2 to 4 carbon atoms, and the substitution position of the sulfo group is the end of the alkoxy group.
- a 4-sulfobutoxy group which is 4-sulfopropoxy group and 4 is more preferable. Particularly preferred is a 3-sulfopropoxy group.
- R 1 to R 6 in the primary and secondary coupling components may have a substituent, and the substituent is not particularly limited.
- the other R 1 to R 6 are each independently 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, Of these, a hydrogen atom, a methyl group, and a methoxy group are preferable.
- the substitution positions of R 1 to R 6 in anilines are not limited.
- only the 2-position, only the 5-position, the combination of the 2-position and the 6-position, the combination of the 2-position and the 5-position, the combination of the 3-position and the 5-position particularly preferably 2 Only -position, 5-position only, 2-position and 5-position combination.
- anilines having an alkoxy group having a sulfo group examples 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- Ethoxyaniline, 3-propoxyaniline, 3-butoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5-dimethylaniline, 2,6-dimethylaniline, 3,5-dimethoxyaniline, etc. Is mentioned.
- anilines having an alkoxy group having a sulfo group include 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 4-aminobenzoic acid, 2-amino- 5-methylbenzenesulfonic acid, 2-amino-5-ethylbenzenesulfonic acid, 2-amino-5-propylbenzenesulfonic acid, 2-amino-5-butylbenzenesulfonic acid, 4-amino-3-methylbenzenesulfonic acid, 4-amino-3-ethylbenzenesulfonic acid, 4-amino-3-propylbenzenesulfonic acid, 4-amino-3-butylbenzenesulfonic acid, 2-amino-5-methoxybenzenesulfonic acid, 2-amino-5-ethoxy Benzenesulfonic acid, 2-amino-5-propyl
- 4-aminobenzenesulfonic acid 2-amino-5-methoxybenzenesulfonic acid
- 4-amino-2-methylbenzenesulfonic acid 4-aminobenzene-1,3-disulfonic acid.
- anilines having a lower alkoxy group having a sulfo group include 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, 3- (2-aminophenoxy) propane-1-sulfonic 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-sulfone Acid, 4- (3-amino-4-methylphenoxy) butane-1-sulfonic acid, 4- (3-aminophenoxy) butane-1-sulfonic acid, 2- (3-amino -4-methylphenoxy) ethane-1-sulfonic acid,
- anilines having an alkoxy group having a sulfo group partially overlapping with the above include 2- (aminophenoxy) ethane-1-sulfonic acid, 3- (4-aminophenoxy) propane- 1-sulfonic acid, 4- (4-aminophenoxy) butane-1-sulfonic acid, 2- (3-aminophenoxy) ethane-1-sulfonic acid, 3- (3-aminophenoxy) propane-1-sulfonic acid, 4- (3-aminophenoxy) butane-1-sulfonic acid, 2-amino-5- (2-sulfoethoxy) benzenesulfonic acid, 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid, 2-amino -5- (4-sulfobutoxy) benzenesulfonic acid, 2-amino-5- (2-sulfoethoxy) benzoic acid, 2-amino-5- (3-sulfopropy)
- 3- (4-aminophenoxy) propane-1-sulfonic acid 3- (3-aminophenoxy) propane-1-sulfonic acid, 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid, 2 -Amino-5- (3-sulfopropoxy) benzoic acid, 3- (4-amino-3-methylphenoxy) propane-1-sulfonic acid, 3- (4-amino-3-methylphenoxy) propane-1-sulfone It is an acid.
- anilines may have an amino group protected.
- protecting group include the ⁇ -methanesulfone group.
- 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 formula (1) or a salt thereof may be contained in a polarizing film substrate (for example, a polymer film) and aligned together with other dyes by a known method, if necessary, mixed with a liquid crystal, or By aligning with a coating method, polarizing films having various colors or neutral colors can be produced.
- 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.
- the 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 molecule, together with 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, and 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 either 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 A1 Add 25.3 parts of 4-aminobenzene-1,3-disulfonic acid to 500 parts of water, cool, add 31.3 parts of 35% hydrochloric acid at 10 ° C. or lower, and then add 6.9 parts of sodium nitrite. The mixture was stirred at 5-10 ° C. for 1 hour to diazotize. Thereto was added 24.5 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, and while stirring at 10-30 ° C., sodium carbonate was added to pH 3, and the mixture was further stirred. The ring reaction was completed and filtered to obtain 45.8 parts of a monoazoamino compound represented by the following formula (M1).
- M1 monoazoamino compound represented by the following formula (M1).
- Example A2 In the same manner as in Example A1, except that 25.3 parts of 4-aminobenzene-1,3-disulfonic acid is changed to 20.3 parts of 2-amino-5-methoxybenzenesulfonic acid, the compound is represented by the above formula (5). 42.0 parts of the ureido compound of the present invention was obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 492 nm.
- Example A3 In the same manner as in Example A1, except that 25.3 parts of 4-aminobenzene-1,3-disulfonic acid was changed to 17.3 parts of 4-aminobenzenesulfonic acid, the compound represented by the above formula (6) was used. 40.2 parts of ureido compound were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 496 nm.
- Example A4 In the same manner as in the primary coupling of Example A1, 55.1 parts of a disazoamino compound represented by the above formula (M1) was obtained.
- Example A5 Similar to the primary coupling of Example A1, except that 24.5 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid were changed to 12.1 parts of 2,5-dimethylaniline. And 34.7 parts of a monoazoamino compound represented by the following formula (M4) were obtained.
- Example A6 Similar to the primary coupling of Example A1, except that 25.3 parts of 4-aminobenzene-1,3-disulfonic acid are changed to 31.1 parts of 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid. Thus, 51.0 parts of a monoazoamino compound represented by the following formula (M6) was obtained.
- Example A7 The same procedure as in Example A6 except that 31.1 parts of 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid was changed to 27.5 parts of 2-amino-5- (3-sulfopropoxy) benzoic acid. Thus, 46.1 parts of the ureido compound of the present invention represented by the above formula (77) was obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 502 nm.
- Example A8 The same procedure as in Example A6 except that 31.1 parts of 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid was changed to 17.3 parts of 4- (4-aminophenoxy) butane-1-sulfonic acid. 40.2 parts of the ureido compound of the present invention represented by the above formula (78) was obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 506 nm.
- Example A9 Similar to the primary coupling of Example A1, except that 25.3 parts of 4-aminobenzene-1,3-disulfonic acid are changed to 31.1 parts of 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid. Thus, 51.0 parts of a monoazoamino compound represented by the following formula (M8) was obtained.
- Example A10 Change 25.3 parts of 4-aminobenzene-1,3-disulfonic acid to 31.1 parts of 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid and 3- (2-amino-4-methylphenoxy) ) Monoazoamino represented by the following formula (M10) in the same manner as in the primary coupling of Example A1, except that 24.5 parts of propane-1-sulfonic acid was changed to 12.1 parts of 2,5-dimethylaniline. 39.9 parts of compound were obtained.
- Example A11 Change 25.3 parts of 4-aminobenzene-1,3-disulfonic acid to 31.1 parts of 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid and 3- (2-amino-4-methylphenoxy) )
- Monoazoamino compound 33 represented by the following formula (M12) in the same manner as in the primary coupling of Example A1, except that 24.5 parts of propane-1-sulfonic acid was changed to 10.7 parts of 3-methylaniline. .4 parts were obtained.
- Example A12 8. 31.1 parts of 2-amino-5- (3-sulfopropoxy) benzenesulfonic acid are added to 27.5 parts of 2-amino-5- (3-sulfopropoxy) benzoic acid and the secondary coupler is 3-methylaniline. 31.5 parts of the ureido compound of the present invention represented by the above formula (149) was obtained in the same manner as in Example A11 except that 6 parts were changed to 12.3 parts of 2-methoxy-5-methylaniline. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 484 nm.
- Examples B1 to B12 Each of the compounds obtained in Examples A1 to A12 (the above formulas (4) to (6), (28), (52), (76) to (78), (100), (124), and (148 ) To (149), a polyvinyl alcohol having a thickness of 75 ⁇ m was immersed in an aqueous solution at 45 ° C. in a concentration of 0.03% and sodium nitrate 0.1% 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. 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. The test method is described below.
- 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 a 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 and the polarization of the absolute polarizer.
- the absorption axis of the film indicates the transmittance when orthogonal.
- the parallel transmittance and orthogonal transmittance at each wavelength were measured at 1 nm intervals from 380 to 780 nm. Using each measured value, 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)
- Test Example As an index representing the image quality, there is a contrast indicating a difference in luminance between white display and black display, and the maximum absorption wavelength of the polarizing film obtained in Examples B1 to B12 and the contrast at that time are displayed. It is shown in 2.
- 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 C1 0.2% of the compound of formula (4) obtained in Example A1, 0.07% of C.I. Direct Orange 39, 0.02% of C.I.
- a polarizing film was prepared in the same manner as in Example B1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
- the maximum absorption wavelength of the obtained polarizing film was 572 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 C2 0.2% of the compound of the formula (28) obtained in Example A4, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and mirabilite 0
- a polarizing film was prepared in the same manner as in Example B4 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
- the maximum absorption wavelength of the obtained polarizing film was 570 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 C3 0.2% of the compound of the formula (52) obtained in Example A5, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and mirabilite 0
- a polarizing film was prepared in the same manner as in Example B5 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
- the maximum absorption wavelength of the obtained polarizing film was 569 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 C4 0.2% of the compound of the formula (76) obtained in Example A6, 0.07% of C.I. Direct Orange 39, 0.02% of C.I. Direct Blue 274, and mirabilite 0
- a polarizing film was prepared in the same manner as in Example B6 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
- the maximum absorption wavelength of the obtained polarizing film was 568 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 C5 0.2% of the compound of the formula (100) obtained in Example A9, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and mirabilite 0
- a polarizing film was prepared in the same manner as in Example B9 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
- the maximum absorption wavelength of the obtained polarizing film was 571 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 C6 0.2% of the compound of the formula (124) obtained in Example A10, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and mirabilite 0
- a polarizing film was prepared in the same manner as in Example B10 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
- the maximum absorption wavelength of the obtained polarizing film was 570 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 C7 0.2% of the compound of the formula (148) obtained in Example A11, 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Blue 274, and mirabilite 0
- a polarizing film was prepared in the same manner as in Example B11 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
- the maximum absorption wavelength of the obtained polarizing film was 568 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。
<1>
下記式(1)
(式中、R1~R6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及びR2は各々独立に水素原子、スルホ基、カルボキシ基、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン基、ニトロ基、アミノ基、炭素数1~4のアルキル置換アミノ基、又は炭素数1~4のアルキル置換アシルアミノ基であり、他のR3~R6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>
式(1)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R1~R6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>
上記式(1)において、R1及びR2の少なくとも1つがスルホ基、カルボキシ基又はスルホ基を有する炭素数1~4のアルコキシ基であり、それが1つである場合には置換基R1及びR2のもう1つは水素原子、スルホ基、カルボキシ基、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン基、ニトロ基、アミノ基、炭素数1~4のアルキル置換アミノ基又は炭素数1~4のアルキル置換アシルアミノ基である<1>又は<2>に記載のアゾ化合物又はその塩、
<4>
式(1)において、(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、(c)R5がスルホ基を有する炭素数1~4のアルコキシ基である、(d)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、(d)R1及びR5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、(e)R3及びR5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、又は(f)R1、R3及びR5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>~<3>のいずれか一項に記載のアゾ化合物又はその塩、
<5>
式(1)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、<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(2)
(式中、R1~R6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2~4のアルコキシ基であり、他のR7及びR8は各々独立に水素原子、スルホ基、カルボキシ基、メチル基、メトキシ基であり、他のR9~R12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、
<7>
式(2)において、スルホ基を有する炭素数2~4のアルコキシ基ではないR9~R12は各々独立に、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>
式(2)において、(a)R7がスルホ基を有する炭素数2~4のアルコキシ基である、(b)R9がスルホ基を有する炭素数2~4のアルコキシ基である、(c)R11がスルホ基を有する炭素数2~4のアルコキシ基である、(d)R7及びR9が各々独立にスルホ基を有する炭素数2~4のアルコキシ基である、(d)R7及びR11が各々独立にスルホ基を有する炭素数2~4のアルコキシ基である、(e)R9及びR11が各々独立にスルホ基を有する炭素数2~4のアルコキシ基である、又は(f)R7、R9及びR11が各々独立にスルホ基を有する炭素数2~4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>
式(2)において、R8がスルホブトキシ基である、<6>~<8>のいずれか一項に記載のアゾ化合物又はその塩、
<10>
式(2)において、スルホ基を有する炭素数2~4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>~<9>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>~<9>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。
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R1~R6の少なくとも1つはスルホ基を有する炭素数1~4のアルコキシ基の炭素数は、好ましくは2~4であり、より好ましくは3、4であり、より好ましくは3である。スルホ基の置換位置は特に限定されないが、好ましくはアルコキシ基の末端である。特に好ましいスルホ基を有する炭素数1~4のアルコキシ基は3-スルホプロポキシ基、4-スルホブトキシ基であり、最も好ましくは3-スルホプロポキシ基である。
他のR1及びR2が水素原子でない場合、他のR1及びR2の少なくとも1つはスルホ基、カルボキシ基であることが好ましい。
ベンゼン環におけるR1及びR2の置換位置は特に限定されないが、好ましくは、2-位のみ、4-位のみ、2-位と6-位の組合せ、2-位と4-位の組合せ、3-位と5-位の組合せであり、さらに好ましくは、2-位のみ、4-位のみ、2-位と4-位の組合せ、又は3-位と5-位の組合せである。なお、前記において、2-位のみ、4-位のみとは、2-位または4-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。
具体的な製造方法としては、下記式(i)で示されるような置換基を有するアニリン類を非特許文献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~R6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-位の組合せが好ましく、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。
4-アミノベンゼンスルホン酸、2―アミノ-5―メトキシベンゼンスルホン酸、4-アミノ-2-メチルベンゼンスルホン酸、4-アミノベンゼン-1,3-ジスルホン酸が特に好ましい。
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 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-スルホン酸が挙げられる。
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-スルホン酸等が挙げられる。
好ましくは、3-(4-アミノフェノキシ)プロパン-1-スルホン酸、4-(4-アミノフェノキシ)ブタン-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-アミノフェノキシ)ブタン-1-スルホン酸、2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸、2-アミノ-5-(4-スルホブトキシ)ベンゼンスルホン酸、2-アミノ-5-(3-スルホプロポキシ)安息香酸、2-アミノ-5-(4-スルホブトキシ)安息香酸、4-アミノ-3-(3-スルホプロポキシ)ベンゼンスルホン酸、4-アミノ-3-(4-スルホブトキシ)ベンゼンスルホン酸、4-アミノ-3-(3-スルホプロポキシ)安息香酸、4-アミノ-3-(4-スルホブトキシ)安息香酸、3-(4-アミノ-3-メチルフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-メチルフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-エチルフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-エチルフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-プロピルフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-プロピルフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-ブチルフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-ブチルフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-メチルフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-メトキシフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-エトキシフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-エトキシフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-プロポキシフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-プロポキシフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-ブトキシフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-ブトキシフェノキシ)ブタン-1-スルホン酸である。
より好ましくは、3-(4-アミノフェノキシ)プロパン-1-スルホン酸、4-(4-アミノフェノキシ)ブタン-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-アミノフェノキシ)ブタン-1-スルホン酸、2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸、2-アミノ-5-(4-スルホブトキシ)ベンゼンスルホン酸、2-アミノ-5-(3-スルホプロポキシ)安息香酸、2-アミノ-5-(4-スルホブトキシ)安息香酸、3-(4-アミノ-3-メチルフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-メチルフェノキシ)ブタン-1-スルホン酸、3-(4-アミノ-3-メチルフェノキシ)プロパン-1-スルホン酸、4-(4-アミノ-3-メトキシフェノキシ)ブタン-1-スルホン酸である。
特に好ましくは3-(4-アミノフェノキシ)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、2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸、2-アミノ-5-(3-スルホプロポキシ)安息香酸、3-(4-アミノ-3-メチルフェノキシ)プロパン-1-スルホン酸、3-(4-アミノ-3-メチルフェノキシ)プロパン-1-スルホン酸である。
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。
4-アミノベンゼン-1,3-ジスルホン酸25.3部を水500部に加え、冷却し10℃以下で、35%塩酸31.3部を加え、次に亜硝酸ナトリウム6.9部を加え、5~10℃で1時間攪拌し、ジアゾ化した。そこへ、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、10~30℃で攪拌しながら、炭酸ナトリウムを加えてpH3とし、さらに攪拌してカップリング反応を完結させ、濾過し、下記式(M1)で示されるモノアゾアミノ化合物45.8部を得た。
4-アミノベンゼン-1,3-ジスルホン酸25.3部から2-アミノ-5-メトキシベンゼンスルホン酸20.3部に変更する以外は実施例A1と同様にして、上記式(5)で示される本発明のウレイド化合物42.0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492nmであった。
4-アミノベンゼン-1,3-ジスルホン酸25.3部から4-アミノベンゼンスルホン酸17.3部に変更する以外は実施例A1と同様にして、上記式(6)で示される本発明のウレイド化合物40.2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496nmであった。
実施例A1の1次カップリングと同様にして上記式(M1)で示されるジスアゾアミノ化合物55.1部を得た。
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2,5-ジメチルアニリン12.1部に変更する以外は実施例A1の1次カップリングと同様にして、下記式(M4)で示されるモノアゾアミノ化合物34.7部を得た。
4-アミノベンゼン-1,3-ジスルホン酸25.3部を2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸31.1部に変更する以外は実施例A1の1次カップリングと同様にして、下記式(M6)で示されるモノアゾアミノ化合物51.0部を得た。
2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸31.1部を2-アミノ-5-(3-スルホプロポキシ)安息香酸27.5部に変更する以外は実施例A6と同様にして、上記式(77)で示される本発明のウレイド化合物46.1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502nmであった。
2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸31.1部から4-(4-アミノフェノキシ)ブタン-1-スルホン酸17.3部に変更する以外は実施例A6と同様にして上記式(78)で示される本発明のウレイド化合物40.2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506nmであった。
4-アミノベンゼン-1,3-ジスルホン酸25.3部を2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸31.1部に変更する以外は実施例A1の1次カップリングと同様にして、下記式(M8)で示されるモノアゾアミノ化合物51.0部を得た。
4-アミノベンゼン-1,3-ジスルホン酸25.3部を2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸31.1部に変更する及び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2,5-ジメチルアニリン12.1部に変更する以外は実施例A1の1次カップリングと同様にして、下記式(M10)で示されるモノアゾアミノ化合物39.9部を得た。
4-アミノベンゼン-1,3-ジスルホン酸25.3部を2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸31.1部に変更する及び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3-メチルアニリン10.7部に変更する以外は実施例A1の1次カップリングと同様にして、下記式(M12)で示されるモノアゾアミノ化合物33.4部を得た。
2-アミノ-5-(3-スルホプロポキシ)ベンゼンスルホン酸31.1部を2-アミノ-5-(3-スルホプロポキシ)安息香酸27.5部に、2次カップラを3-メチルアニリン9.6部から2-メトキシ-5-メチルアニリン12.3部に変更する以外は実施例A11と同様にして、上記式(149)で示される本発明のウレイド化合物31.5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484nmであった。
実施例A1~A12で得られた各々の化合物(上記式(4)~(6)、(28)、(52)、(76)~(78)、(100)、(124)、及び(148)~(149)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。
なお、試験方法を以下に記す。
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乃至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。
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B1~B12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5中の実施例1に記載された方法と同様に合成した化合物(II-5)を用いて、本発明の実施例B1~B12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、偏光性能が優れていた。
実施例A1で得られた式(4)の化合物を染料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B1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572nm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A4で得られた式(28)の化合物を染料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B4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570nm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A5で得られた式(52)の化合物を染料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B5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569nm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A6で得られた式(76)の化合物を染料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B6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568nm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A9で得られた式(100)の化合物を染料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B9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571nm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A10で得られた式(124)の化合物を染料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B10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570nm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A11で得られた式(148)の化合物を染料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B11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568nm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)
- 式(1)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R1~R6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、
- 上記式(1)において、R1及びR2の少なくとも1つがスルホ基、カルボキシ基又はスルホ基を有する炭素数1~4のアルコキシ基であり、それが1つである場合には置換基R1及びR2のもう1つは水素原子、スルホ基、カルボキシ基、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン基、ニトロ基、アミノ基、炭素数1~4のアルキル置換アミノ基又は炭素数1~4のアルキル置換アシルアミノ基である請求項1又は2に記載のアゾ化合物又はその塩、
- 式(1)において、(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、(c)R5がスルホ基を有する炭素数1~4のアルコキシ基である、(d)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、(d)R1及びR5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、(e)R3及びR5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、又は(f)R1、R3及びR5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1~3のいずれか一項に記載のアゾ化合物又はその塩、
- 式(1)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1~4のいずれか一項に記載のアゾ化合物又はその塩、
- 式(2)において、スルホ基を有する炭素数2~4のアルコキシ基ではないR9~R12は各々独立に、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、
- 式(2)において、(a)R7がスルホ基を有する炭素数2~4のアルコキシ基である、(b)R9がスルホ基を有する炭素数2~4のアルコキシ基である、(c)R11がスルホ基を有する炭素数2~4のアルコキシ基である、(d)R7及びR9が各々独立にスルホ基を有する炭素数2~4のアルコキシ基である、(d)R7及びR11が各々独立にスルホ基を有する炭素数2~4のアルコキシ基である、(e)R9及びR11が各々独立にスルホ基を有する炭素数2~4のアルコキシ基である、又は(f)R7、R9及びR11が各々独立にスルホ基を有する炭素数2~4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、
- 式(2)において、R8がスルホブトキシ基である、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、
- 式(2)において、スルホ基を有する炭素数2~4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1~9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1~9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、
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WO2021153374A1 (ja) * | 2020-01-29 | 2021-08-05 | 日本化薬株式会社 | アゾ化合物又はその塩、並びにこれを含有する染料系偏光膜、染料系偏光板、及び表示装置 |
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