[go: up one dir, main page]

WO2018181470A1 - Composé azoïque ou sel de celui-ci, et film polarisant à base de colorant, plaque polarisante à base de colorant et appareil d'affichage à cristaux liquides contenant celle-ci - Google Patents

Composé azoïque ou sel de celui-ci, et film polarisant à base de colorant, plaque polarisante à base de colorant et appareil d'affichage à cristaux liquides contenant celle-ci Download PDF

Info

Publication number
WO2018181470A1
WO2018181470A1 PCT/JP2018/012737 JP2018012737W WO2018181470A1 WO 2018181470 A1 WO2018181470 A1 WO 2018181470A1 JP 2018012737 W JP2018012737 W JP 2018012737W WO 2018181470 A1 WO2018181470 A1 WO 2018181470A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
dye
sulfo
azo compound
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/012737
Other languages
English (en)
Japanese (ja)
Inventor
由侑 服部
貴大 樋下田
光則 中村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Polatechno Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Polatechno Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd, Polatechno Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to KR1020197027526A priority Critical patent/KR20190134615A/ko
Priority to JP2019509971A priority patent/JP7035018B2/ja
Priority to CN201880009570.3A priority patent/CN110249008B/zh
Publication of WO2018181470A1 publication Critical patent/WO2018181470A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • 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
    • C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
    • 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 aazo compound or a salt thereof, and a dye-based polarizing film, a dye-based polarizing plate, and a liquid crystal display device containing the same.
  • 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
  • the application fields of this LCD include small devices 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.
  • polarizing plates Since the applications of polarizing plates as described above are widespread, polarizing plates are used in a wide range of conditions from low temperature to high temperature, low humidity to high humidity, low light intensity to high light intensity, so high polarization performance and high durability There is a need for a polarizing plate having a property.
  • polarizing plates are used for polarizing film substrates such as stretched and oriented films of polyvinyl alcohol or derivatives thereof, polyene films formed by dehydrochlorination of polyvinyl chloride films or dehydration of polyvinyl alcohol films, and the like. 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 in a high temperature and high humidity state.
  • 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, when the polarizing film is mounted on a liquid crystal panel In the dark state, the hue of the liquid crystal display may change. 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. In such a polarizing film, the orthogonal transmittance (orthogonal transmittance) in the wavelength region of the visible light region must be uniformly reduced.
  • in-vehicle liquid crystal displays which are in a high temperature and high humidity environment in a summer car, there is a demand for a polarizing plate that does not change the degree of polarization even in a harsh environment.
  • 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 for the production of the above dye-based polarizing film include water-soluble azo compounds described in Patent Document 1 to Patent Document 6, and the like.
  • One of the objects of the present invention is to provide a novel polarizing plate. Another object of the present invention is to provide a polarizing plate having excellent polarization performance. Another object of the present invention is to provide a polarizing plate having durability (moisture resistance, heat resistance, or light resistance). Furthermore, another object of the present invention is a polarizing plate exhibiting a neutral gray formed by adsorbing and orienting two or more kinds of dichroic dyes on a polymer film, wherein the color is orthogonal in the wavelength region of the visible light region. An object of the present invention is to provide a polarizing plate having no polarization and excellent polarization performance.
  • a further object is a dye-based neutral gray polarizing plate for in-vehicle liquid crystal displays, which provides a high-performance polarizing plate with good brightness, polarization performance, and durability (moisture resistance, heat resistance, or light resistance). There is.
  • a 1 and A 2 are each independently a naphthyl group which may have a substituent selected from the group consisting of a hydroxy group, a C1-4 alkoxy group having a sulfo group, and a sulfo group, or a substituted group.
  • a phenyl group which may have a group, R 1 to R 6 are each independently a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a C1-4 alkoxy group having a sulfo group, a carboxy group, a hydroxy group, a halogen group, or a C1-4 alkyl-substituted acylamino.
  • Base Or a salt thereof.
  • a 1 and A 2 (if both are independently), a sulfo group, a carboxy group, a C1-4 alkoxy group having a sulfo group, a C1-4 alkyl group, a C1-4 alkoxy group , Halogen group, nitro group, amino group, N, N-dimethylamino group, N, N-diethylamino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group
  • a 1 and A 2 have at least one substituent selected from a sulfo group, a carboxy group, and a C1-4 alkoxy group having a sulfo group.
  • a 1 and A 2 (if both are independently), the following formula (2): (In the formula, one of R 7 and R 8 is a C1-4 alkoxy group having a sulfo group, a carboxyl group, or a sulfo group, and the other is a C1-4 alkoxy group having a hydrogen atom, a sulfo group, a carboxy group, or a sulfo group.
  • the azo compound or a salt thereof according to any one of (1) to (3), which is a phenyl group represented by the formula: (5)
  • a 1 and A 2 (if both are independently), the following formula (3): (Wherein R 9 is a hydrogen atom, a hydroxy group, a C1-4 alkoxy group having a sulfo group, or a sulfo group, and n is an integer of 1 to 3)
  • R 9 is a hydrogen atom, a hydroxy group, a C1-4 alkoxy group having a sulfo group, or a sulfo group, and n is an integer of 1 to 3
  • R 1 to R 6 are as defined in formula (1)
  • R 1 to R 6 are each independently a C1-4 alkoxy group having a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a halogen group, or a sulfo group (1) to (11) Or an azo compound according to any one of the above.
  • R 1 to R 6 are each independently a C1-4 alkoxy group having a sulfo group, a hydrogen atom, a methyl group, an ethyl group, a halogen group, or a methoxy group, and any one of (1) to (12) An azo compound or a salt thereof.
  • a dye-based polarizing film comprising a polarizing film substrate containing the azo compound or salt thereof according to any one of (1) to (15).
  • a dye-based polarizing film comprising a polarizing film substrate containing the azo compound or a salt thereof according to any one of (1) to (15) and one or more organic dyes other than these.
  • a polarizing plate for liquid crystal display comprising the dye-based polarizing film according to any one of (16) to (18) or the dye-based polarizing plate according to (19).
  • a neutral gray polarizing plate comprising the dye-based polarizing film according to any one of (16) to (18) or the dye-based polarizing plate according to (19).
  • a liquid crystal display device comprising the dye-based polarizing plate according to (19), the polarizing plate for liquid crystal display according to (20), or the neutral gray polarizing plate according to (21).
  • the azo compound or a salt thereof of the present invention is useful as a dye for a polarizing film.
  • the polarizing film of this invention containing the said azo compound or its salt has a high polarizing performance comparable to the polarizing film using an iodine.
  • the polarizing film of the present invention is also excellent in durability (constitution, heat resistance, or light resistance). 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 following formula (1).
  • a 1 and A 2 are each independently a naphthyl group which may have a substituent, or a phenyl group having a substituent. In one embodiment, both A 1 and A 2 are phenyl groups. In another embodiment, at least one of A 1 and A 2 is an optionally substituted naphthyl group. When both A 1 and A 2 are naphthyl groups which may have a substituent, the substituents which the naphthyl group has may be the same or different. When both A 1 and A 2 are phenyl groups which may have a substituent, the substituents which the phenyl group has may be the same or different. In the specification and claims of the present application, “lower” in “lower alkyl” and “lower alkoxy” represents 1 to 4 carbon atoms. It is also expressed as “C1-4”.
  • the phenyl group having a substituent is preferably a sulfo group, a carboxy group, a lower alkoxy group having a sulfo group, a lower alkyl group, a lower alkoxy group, a halogen group, a nitro group, an amino group, a lower alkyl-substituted amino group, and a lower group.
  • An alkyl-substituted acylamino group is a phenyl group having one or more substituents selected from the group consisting of phenyl groups.
  • the phenyl group has two or more substituents
  • at least one of the substituents is preferably a sulfo group, a carboxy group, or a lower alkoxy group having a sulfo group.
  • Other substituents are sulfo group, hydrogen atom, lower alkyl group, lower alkoxy group, lower alkoxy group having sulfo group, carboxy group, chloro group, bromo group, nitro group, amino group, lower alkyl-substituted amino group, or A lower alkyl-substituted acylamino group is preferred.
  • the other substituents are sulfo group, hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, carboxy group, sulfoethoxy group, sulfopropoxy group, sulfobutoxy group, chloro group, nitro group, amino group.
  • the substitution position is not particularly limited, but preferably only 2-position, only 4-position, combination of 2-position and 6-position, combination of 2-position and 4-position, and combination of 3-position and 5-position Particularly preferred are 2-position only, 4-position only, a combination of 2-position and 4-position, or a combination of 3-position and 5-position.
  • the 2-position only and 4-position only indicate that the 2-position or 4-position only has one substituent other than a hydrogen atom.
  • the phenyl group having a substituent is preferably represented by the following formula (2).
  • One of R 7 and R 8 is a lower alkoxy group having a sulfo group, a carboxyl group, or a sulfo group, and the other is a lower alkoxy group having a hydrogen atom, a sulfo group, a carboxy group, or a sulfo group, a lower alkyl group, or a lower alkoxy group.
  • one of R 7 and R 8 is a sulfo group or a carboxy group, and the other is a hydrogen atom, a sulfo group, a carboxy group, a methyl group, or a methoxy group.
  • the naphthyl group which may have a substituent is preferably a naphthyl group which may have one or more substituents selected from the group consisting of a hydroxy group, a lower alkoxy group having a sulfo group, and a sulfo group. .
  • the naphthyl group which may have a substituent is preferably a naphthyl group represented by the following formula (3).
  • R 9 is a hydrogen atom, a hydroxy group, a lower alkoxy group having a sulfo group, or a sulfo group.
  • n is an integer of 1 to 3.
  • the position of the sulfo group may be present in any benzene nucleus of the naphthalene ring.
  • R 9 is a hydrogen atom and n is 2.
  • 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.
  • the lower alkoxy group having a sulfo group is more preferably a 3-sulfopropoxy group and a 4-sulfobutoxy group.
  • the position of the substituent that the naphthyl group has is not particularly limited, but as explained by the number shown in Formula (3), in the case of two substituents, the 5-position and the 7-position, or the 6-position and the 8-position A combination is preferred, and when there are three substituents, the 3-position, 5-position and 7-position, and the 3-position, 6-position and 8-position are preferred.
  • R 1 to R 6 are not particularly limited, but preferably each independently a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group having a sulfo group, a carboxy group, a hydroxy group, a halogen group, or a lower alkyl-substituted acylamino It is a group.
  • R 1 to R 6 are each independently preferably a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group having a sulfo group, or a halogen group, more preferably a hydrogen atom, a methyl group, an ethyl group, A methoxy group, an ethoxy group, a chloro group, a fluorine group, a 3-sulfopropoxy group, or a 4-sulfobutoxy group, and more preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or a 3-sulfopropoxy group. is there.
  • At least one of R 1 to R 6 is a lower alkoxy group having a sulfo group.
  • the lower alkoxy group having a sulfo group is preferably a C2-4 alkoxy group, more preferably a C3-4 alkoxy group, and particularly preferably a C3 alkoxy group.
  • the substitution position of the sulfo group is not particularly limited, but is preferably the terminal of the alkoxy group.
  • Particularly preferred C1-4 alkoxy groups 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 lower alkoxy group having a sulfo group, may be a lower alkoxy group having an R 3 sulfo group, R 5 may be a lower alkoxy group having a sulfo group, and R 1 and R 3 may be independently a lower alkoxy group having a sulfo group, R 1 and R 5 may be each independently a lower alkoxy group having a sulfo group, and R 3 and R 5 are each independently May be a lower alkoxy group having a sulfo group, or R 1, R 3 and R 5 may be each independently a lower alkoxy group having a sulfo group.
  • none of R 1 to R 6 is a C1-4 alkoxy group having a sulfo group.
  • the positions of R 1 to R 6 are preferably 2-position only, 5-position only, 2-position and 6-position combination, 2-position and 5-position combination, 3-position and 5-position
  • the combination of the 2-position, the 5-position only, the 2-position and 5-position combination is more preferable.
  • the 2-position only and the 5-position only indicate that only one substituent other than a hydrogen atom is present at the 2-position or 5-position only.
  • a 1 and A 2 are each independently a naphthyl group which may have a substituent selected from the group consisting of a hydroxy group, a C1-4 alkoxy group having a sulfo group, and a sulfo group, or a substituted group
  • a phenyl group which may have a group, except that both A 1 and A 2 are phenyl groups having a substituent
  • R 1 to R 6 are each independently a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a C1-4 alkoxy group having a sulfo group, a carboxy group, a hydroxy group, a halogen group, or a C1-4 alkyl-substituted acylamino. It is a group.
  • a 1 and A 2 are each independently a phenyl group which may have a substituent
  • R 1 to R 6 are each independently a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxy group, a halogen group, or a C1-4 alkyl-substituted acylamino group.
  • a 1 and A 2 are each independently a phenyl group which may have a substituent
  • At least one of R 1 to R 6 is a C1-4 alkoxy group having a sulfo group
  • the rest are each independently a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a carboxy group, a hydroxy group, or a halogen group.
  • a C1-4 alkyl-substituted acylamino group are each independently a phenyl group which may have a substituent
  • At least one of R 1 to R 6 is a C1-4 alkoxy group having a sulfo group
  • the rest are each independently a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a carboxy group, a hydroxy group, or a halogen group.
  • a C1-4 alkyl-substituted acylamino group are each independently a phenyl group which may have
  • the azo compound represented by the formula (1) is preferably represented by the following formula (4).
  • the azo compound represented by formula (1) is preferably represented by formula (5).
  • At least one of R 10 to R 13 is a sulfo group, and the other represents a hydrogen atom, a sulfo group, a carboxyl group, a C1-4 alkoxy group having a sulfo group, a methyl group, or a methoxy group.
  • R 1 to R 6 are as defined in formula (1).
  • both A 1 and A 2 are phenyl groups, and none of R 1 to R 6 is a lower alkoxy group having a sulfo group, are given below.
  • both A 1 and A 2 are phenyl groups and at least one of R 1 to R 6 is a lower alkoxy group having a sulfo group will be given below.
  • the azo compound represented by the formula (1) may be in a free acid form or a salt form.
  • salts include alkali salts such as lithium salts, sodium salts, and potassium salts, ammonium salts, and organic salts such as amine salts, with sodium salts being preferred.
  • the azo compound represented by the formula (1) or a salt thereof is subjected to diazotization and coupling in accordance with a normal method for producing an azo dye as described in Non-Patent Document 1, and as described in Patent Document 3. It can be produced by reacting with a ureido agent.
  • an aniline having a substituent represented by the following formula (i) is diazotized by the same production method as in Non-Patent Document 1, and coupled with an aniline of the following formula (ii).
  • a monoazoamino compound represented by the following formula (iii) is obtained by the following formula (iii).
  • 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).
  • anilines having a substituent represented by the following formula (vi) are diazotized by the same method as in Non-Patent Document 1, coupled with anilines of the following formula (vii), and represented by the following formula (viii) To obtain a monoazoamino compound.
  • a 2 represents the same meaning as in the above formula (1).
  • the azo compound of formula (1) is obtained by reacting the disazoamino compound (v) and the monoazoamino compound (viii) with a ureido agent such as phenyl chloroformate.
  • the diazotization step is performed by, for example, a conventional method of mixing a nitrite such as sodium nitrite into a mineral acid aqueous solution or suspension of diazo component such as hydrochloric acid or sulfuric acid, or a neutral or weak alkaline aqueous solution of diazo component. Nitrite is added to the mixture, and this is mixed with mineral acid.
  • the diazotization temperature is suitably -10 to 40 ° C.
  • the coupling step with anilines is preferably 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. under acidic conditions of pH 2 to 7.
  • the disazoamino compound (v) and monoazoamino compound (viii) obtained by the coupling can be precipitated by aciding out or salting out and filtered or taken out to the next step as a solution or suspension. . If the diazonium salt is insoluble and in suspension, it can be filtered and used as a press cake in the next coupling step.
  • Specific conditions for the ureido reaction of the disazoamino compound (v) and the monoazoamino compound (viii) using a ureido agent are, for example, a temperature of 10 to 10 according to the production method shown on page 57 of Patent Document 3.
  • the temperature is preferably 90 ° C. and pH 3 to 11, more preferably 20 to 80 ° C., pH 4 to 10, and particularly preferably 20 to 70 ° C. and pH 6 to 9.
  • ureido agents include phenyl chloroformate, phosgene, triphosgene, ethyl chloroformate, butyl chloroformate, isobutyl chloroformate, 4-nitrophenyl chloroformate, 4-fluorophenyl chloroformate, 4-chlorophenyl chloroformate, and chloroformate.
  • 4-Bromophenyl, diphenyl carbonate, bis (2-methoxyphenyl) carbonate, bis (pentafluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, and 1,1′-carbonyldiimidazole can be used. It is not limited to.
  • the ureido agent is preferably phenyl chloroformate, 4-nitrophenyl chloroformate, 4-chlorophenyl chloroformate, diphenyl carbonate, bis (4-nitrophenyl) carbonate, and more preferably phenyl chloroformate, chloroformate 4 -Nitrophenyl.
  • the obtained azo compound of the formula (1) 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.
  • organic solvent used for purification include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
  • the aromatic amines represented by A 1 —NH 2 and A 2 —NH 2 which are starting materials for synthesizing the azo compound represented by the formula (1) are naphthylamines or anilines.
  • naphthylamines having one or more selected from the group consisting of a hydrogen atom, a hydroxy group, a lower alkoxy group having a sulfo group, and a sulfo group are preferably used.
  • naphthylamines include 4-aminonaphthalenesulfonic acid, 7-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid, and 7-aminonaphthalene-1.
  • naphthylamines having a sulfo group and a lower alkoxy group having a sulfo group examples include 7-amino-3- (3-sulfopropoxy) naphthalene-1-sulfonic acid and 7-amino-3- (4-sulfobutoxy).
  • Naphthalene-1-sulfonic acid 7-amino-4- (3-sulfopropoxy) naphthalene-2-sulfonic acid, 7-amino-4- (4-sulfobutoxy) naphthalene-2-sulfonic acid, 6-amino-4 -(3-sulfopropoxy) naphthalene-2-sulfonic acid, 6-amino-4- (4-sulfobutoxy) naphthalene-2-sulfonic acid, 2-amino-5- (3-sulfopropoxy) naphthalene-1,7 -Disulfonic acid, 6-amino-4- (3-sulfopropoxy) naphthalene-2,7-disulfonic acid, 7-amino-3- (3-sulfop Epoxy), and naphthalene-1,5-disulfonic acid.
  • anilines include 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 4-aminobenzoic acid, 2-amino-5-methylbenzenesulfonic acid, 2-amino-5-ethylbenzene Sulfonic 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-ethoxybenzenesulfonic acid, 2-amino-5-propoxybenzenesulfonic acid 2-amino-5-butoxy
  • Aromatic amines (ii), (iv) and (vii) which are primary and 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-ethoxyaniline, 3-propoxyaniline, 3-butoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5-dimethylaniline, 2,6- Dimethylaniline, 3,5-dimethoxyaniline, 5-chloro-2-methoxyaniline, 5-chloro B-2-Ethoxyaniline, 5-chloro-2-propoxyaniline, 5-chloro-2-butoxyaniline, 5-fluor
  • the dye-based polarizing film includes a polarizing film substrate containing an azo compound represented by the formula (1) or a salt thereof as a dichroic dye.
  • the dye-based polarizing film can be either a neutral gray polarizing film or a color polarizing film, and is preferably a neutral gray polarizing film.
  • neutral gray is a specific wavelength in the wavelength region of the visible light region in a state in which two polarizing films are superposed so that their orientation directions are orthogonal to each other (hereinafter also referred to as “orthogonal position”). Means less light leakage (color leakage).
  • the dye-based polarizing film contains one or more kinds of azo compounds represented by the formula (1) or a salt thereof as a dichroic dye, and further contains one or more other organic dyes as necessary. be able to.
  • the other organic dye 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 represented by the formula (1) or a salt thereof and having high dichroism. Examples of other organic dyes include C.I. Eye. direct. Yellow 12, sea. Eye. direct. Yellow 28, Sea. Eye. direct. Yellow 44, Sea. Eye. direct. Orange 26, Sea. Eye. direct. Orange 39, sea. Eye. direct. Orange 71, Sea. Eye. direct. Orange 107, sea. Eye. direct. Red 2, sea. Eye. direct.
  • alkali metal salts for example, Na salt, K salt, Li salt
  • the types of organic dyes to be blended differ depending on whether the target polarizing film is a neutral gray polarizing film, a color polarizing film for liquid crystal projectors, or other color polarizing films.
  • the blending ratio is not particularly limited, but generally, the total of at least one other organic dye is 0.01% with respect to 1 part by mass of the azo compound of the formula (1) or a salt thereof. It is preferably used in the range of ⁇ 100 parts by mass, more preferably in the range of 0.1 ⁇ 10 parts by mass.
  • the types and blending ratios of other organic dyes to be used are adjusted so that color leakage in the wavelength region of the visible light region of the obtained polarizing film is reduced. .
  • the target polarizing film When the target polarizing film is a color polarizing film, it has a high single plate average light transmittance in a specific wavelength region of the obtained polarizing film, and a specific light transmittance at a perpendicular position is low, for example, a specific polarizing film
  • the type and blending ratio of other organic dyes used in combination are adjusted so as to have a single plate average light transmittance of 39% or more in the wavelength region and an average light transmittance of 0.4% or less in the orthogonal position. .
  • the dye-based polarizing film is a known dichroic dye containing an azo compound represented by the formula (1) or a salt thereof and, if necessary, another dye as a polarizing film substrate (for example, a polymer film). It can be produced by containing and aligning by the above method, mixing with liquid crystal, or aligning by a coating method.
  • the polarizing film substrate is preferably a polymer film, and more preferably a film made of polyvinyl alcohol resin or a derivative thereof.
  • Specific examples of the polarizing film substrate include polyvinyl alcohol resin or derivatives thereof, and modified with olefins such as ethylene and propylene, and unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, and maleic acid. And the like.
  • a film made of polyvinyl alcohol resin or a derivative thereof is preferably used from the viewpoint of the adsorptivity and orientation of the dye.
  • the thickness of the polarizing film substrate is usually about 10 to 100 ⁇ m, preferably about 20 to 80 ⁇ m.
  • a method of dyeing the polymer film is usually employed to contain the azo compound of formula (1) or a salt thereof.
  • the staining is performed as follows. First, a dye bath is prepared by dissolving an azo compound represented by the formula (1) or a salt thereof and, if necessary, other organic 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. If necessary, a dyeing assistant may be used. For example, it is preferable to use mirabilite at a concentration of, for example, about 0.1 to 10% by mass.
  • Dyeing can be performed by immersing the polymer film in the dyeing bath thus prepared, for example, for 1 to 10 minutes.
  • the dyeing temperature is preferably about 30 to 80 ° C.
  • the orientation of the azo compound represented by the formula (1) or a salt thereof is performed by stretching a polymer film dyed with a dichroic dye.
  • the draw ratio is generally 2 to 8 times, but is not limited, and preferably 3 to 7.5 times, more preferably 4 to 7 times.
  • 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, for example, 0.1 to 15% by mass, preferably 1 to 10% by mass.
  • the treatment is performed 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 dye-based polarizing film includes, for example, liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments and displays, and lenses and glasses.
  • the dye-based polarizing film has high polarization performance comparable to a polarizing film using iodine, and is excellent in durability. For this reason, it is particularly suitable for various liquid crystal display bodies and liquid crystal projectors for applications requiring high polarization performance and durability, for example, for in-vehicle use and outdoor display (for example, display for industrial instruments and wearable use). is there.
  • the dye-based polarizing plate can be obtained by pasting a transparent protective film on one side or both sides of the dye-based polarizing film. Since the dye-based polarizing plate includes the above-described dye-based polarizing film, the dye-based polarizing plate has excellent polarization performance, moisture resistance, heat resistance, and light resistance.
  • the material for forming the transparent protective film is preferably a material excellent in optical transparency and mechanical strength, such as a cellulose acetate film, an acrylic film, a tetrafluoroethylene / hexafluoropropylene copolymer, etc.
  • a film made of a fluorine-based film, a polyester resin, a polyolefin resin, or a polyamide-based resin is used.
  • the transparent protective film is preferably a triacetyl cellulose (TAC) film or a cycloolefin film.
  • TAC triacetyl cellulose
  • the thickness of the protective film is usually preferably 40 to 200 ⁇ m.
  • adhesives that can be used to bond the dye-based polarizing film and the protective film include polyvinyl alcohol adhesives, urethane emulsion adhesives, acrylic adhesives, and polyester-isocyanate adhesives. System adhesives are preferred.
  • a transparent protective layer may be further provided on the surface of the dye-based polarizing plate.
  • the further transparent protective layer include an acrylic or polysiloxane hard coat layer and a urethane protective layer.
  • an AR layer antireflection 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-based polarizing plate preferably further includes a support.
  • the dye-based polarizing plate can be used as an elliptical polarizing plate by attaching a retardation plate to the surface.
  • the dye-based polarizing plate may be either a neutral gray polarizing plate or a color polarizing plate depending on the application.
  • Neutral gray polarizing plate has a neutral color, has little orthogonal color leakage in the polarization region of the visible light region, has excellent polarization performance, and is resistant to discoloration and deterioration of polarization performance even in high temperature and high humidity conditions. Because of its high performance, it is suitable for in-vehicle use or outdoor display.
  • the neutral gray polarizing plate for in-vehicle use or outdoor display is provided with an AR layer on a polarizing plate composed of a dye-based polarizing film and a transparent protective film to further improve the single light transmittance. It is preferable that the AR layer and the polarizing plate with a support on which both the AR layer and a support such as a transparent resin are attached are more preferable.
  • the AR layer can be provided on one side or both sides of the polarizing plate.
  • the support is preferably provided on one side of the polarizing plate, and may be provided directly on the polarizing plate, or the support may be provided with a polarizing plate with an AR layer (AR layer / polarizing plate / AR layer). .
  • the AR layer and the polarizing plate with a support preferably include AR layer / polarizing plate / AR layer / support in this order.
  • the support preferably has a flat part for attaching the polarizing plate, and is preferably a transparent substrate because it is used for optical purposes.
  • the transparent substrate is roughly divided into an inorganic substrate and an organic substrate, inorganic substrates such as soda glass, borosilicate glass, crystal substrate, sapphire substrate, and spinel substrate, and acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and Although organic substrates, such as a cycloolefin polymer, are mentioned, an organic substrate is preferable.
  • the thickness and size of the transparent substrate may be a desired size.
  • a color polarizing plate is suitable for liquid crystal projectors and display devices such as in-vehicle and outdoor displays because it has excellent polarization performance and does not cause discoloration or deterioration of polarization performance even in a high-temperature and high-humidity state.
  • a color polarizing plate for a liquid crystal projector has brightness and excellent polarization performance.
  • a necessary wavelength range of the polarizing plate (A. When using an ultra-high pressure mercury lamp; 420 to 500 nm for a blue channel, 500 to 500 green channels) 580 nm, red channel 600-680 nm, peak wavelength when using B.3 primary color LED lamp: blue channel 430-450 nm, green channel 520-535 nm, red channel 620-635 nm) 39% or more, the average light transmittance in the 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% or less. More preferably, 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 single-plate average light transmittance is a specific wavelength region when natural light is incident on one polarizing plate (hereinafter also simply referred to as “polarizing plate”) not provided with a support such as an AR layer and a transparent glass plate. It is the average value of the light transmittance in.
  • the average light transmittance at the orthogonal position is an average value of light transmittance in a specific wavelength region when natural light is incident in a state where two polarizing plates are superposed so that their orientation directions are orthogonal to each other.
  • the polarizing film used for the color polarizing plate for in-vehicle use or outdoor display may be provided with a protective layer or an AR layer and a support, etc., if necessary, on the dye-based polarizing plate, as with the neutral gray polarizing plate.
  • the support-attached color polarizing plate can be obtained, for example, by applying a transparent adhesive (adhesive) agent on the flat surface of the support, and then attaching a dye-based polarizing plate to the coated surface.
  • a transparent adhesive (adhesive) agent may be applied to the dye-based polarizing plate, and then a support may be attached to the coated surface.
  • the adhesive (adhesive) agent is preferably, for example, an acrylic ester-based one.
  • this dye-based polarizing plate is used as an elliptical polarizing plate, it is usual that the retardation plate side is attached to a support and the lamination order of the dye-based polarizing plate / retardation plate / support is set.
  • the polarizing plate side may be attached to the support, and the retardation plate / polarizing plate / support may be laminated.
  • a liquid crystal display device includes the dye-based polarizing film or the dye-based polarizing plate.
  • the liquid crystal display device is used for displays such as calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring instruments and displays, and particularly requires high polarization performance and durability. It is suitably used for various liquid crystal display bodies, for example, for in-vehicle use or for outdoor display (for example, display use for industrial instruments or wearable use).
  • the dye-based polarizing film or the dye-based polarizing plate provided in the liquid crystal display device is preferably neutral gray.
  • a dye-based polarizing plate is disposed on either or both of the incident side and the emission side of the liquid crystal cell.
  • the dye-based 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 liquid crystal cell can be used as a support for the dye-based polarizing plate.
  • the dye-based polarizing plate is not in contact with the liquid crystal cell, it is preferable to use a dye-based polarizing plate provided with a support other than the liquid crystal cell.
  • a dye-type polarizing plate is disposed on both the incident side and the emission side of the liquid crystal cell. Further, the polarizing plate surface of the dye-type polarizing plate is on the liquid crystal cell side, and the support surface is It is preferable to arrange on the light source 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.
  • a liquid crystal cell included in a liquid crystal display device is, for example, an active matrix type, and is formed by sealing liquid crystal between a transparent substrate on which electrodes and TFTs are formed and a transparent substrate on which counter electrodes are formed. It is preferable.
  • Light emitted from a light source such as a cold-cathode tube lamp or a white LED passes through a dye-based polarizing plate, and then passes through a liquid crystal cell, a color filter, and further a dye-based polarizing plate and is projected on a display screen.
  • the liquid crystal display device has high brightness and excellent polarization performance as well as polarization and light resistance, so it is difficult to cause discoloration or deterioration of polarization performance even in high temperature and high humidity conditions such as in a car or outdoors. high.
  • Example E1 Synthesis of azo compound of formula (A-3) Add 30.3 parts of 7-aminonaphthalene-1,3-disulfonic acid to 500 parts of water, cool and 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 -10 ° C for 1 hour to diazotize. Thereto, 12.3 parts of 2-methoxyaniline was added and stirred at 10-30 ° C., sodium carbonate was added to adjust the pH to 3, further stirring to complete the coupling reaction, filtration, and the following formula (A-3M) 30.6 parts of a monoazoamino compound represented by the formula:
  • Example E2 Synthesis of azo compound of formula (A-6) Add 24.2 parts of 7-aminonaphthalene-1,3-disulfonic acid to 400 parts of water, cool and add 25.0 parts of 35% hydrochloric acid at 10 ° C. or lower, then add 5.5 parts of sodium nitrite and add 5 parts. The mixture was stirred at -10 ° C for 1 hour to diazotize. Thereto was added 8.6 parts of 2-methylaniline, and while stirring at 10-30 ° C., sodium carbonate was added to adjust the pH to 3, further stirring to complete the coupling reaction, filtration, and the following formula (A-6MR) 23.6 parts of a monoazoamino compound represented by the formula:
  • Example E3 Synthesis of azo compound of formula (A-19) Add 29.5 parts of monoazoamino compound (A-6MR) to 400 parts of water, dissolve with sodium hydroxide, add 21.9 parts of 35% hydrochloric acid at 10-30 ° C., then add 4.8 parts of sodium nitrite. In addition, the mixture was stirred at 20 to 30 ° C. for 1 hour to diazotize. Thereto was added 17.2 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, and while stirring at 20 to 30 ° C., sodium carbonate was added to pH 4, and the mixture was further stirred. The ring reaction was completed and filtered to obtain 38.0 parts of a disazoamino compound represented by the following formula (A-19D).
  • Example E4 Synthesis of azo compound of formula (A-20)
  • Example E3 except that 16.2 parts of 3- (2-aminophenoxy) propane-1-sulfonic acid were used instead of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid
  • 11.2 parts of a ureido compound represented by the above formula (A-20) was obtained.
  • the maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 430 nm.
  • Example E5 Synthesis of azo compound of formula (A-32) A ureido represented by the above formula (A-32) was obtained in the same manner as in Example E1, except that 9.3 parts of aniline was used instead of 2-methoxyaniline which is a raw material of the disazoamino compound (A-3D). 10.2 parts of compound were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 440 nm.
  • Example E6 Synthesis of azo compound of formula (A-36) Except that 8.5 parts of 2,5-dimethylaniline was used in place of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, the above formula (A 9.0 parts of a ureido compound represented by -36) were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 416 nm.
  • Example E7 Synthesis of azo compound of formula (A-130) Add 11.0 parts of 4-aminobenzoic acid to 300 parts of water, cool and add 25.0 parts of 35% hydrochloric acid at 10 ° C. or lower, then add 5.5 parts of sodium nitrite and add at 5-10 ° C. for 1 hour. Stir and diazotize. Thereto was added 11.0 parts of 2-methoxy-5-methylaniline, and while stirring at 10-30 ° C., sodium carbonate was added to adjust the pH to 3, further stirring to complete the coupling reaction, filtration, and the following formula ( A-130MR) was obtained, 16.0 parts of a monoazoamino compound.
  • Example E8 Synthesis of azo compound of formula (A-61) 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, 12.1 parts of 2,5-dimethylaniline was added, and while stirring at 10-30 ° C., sodium carbonate was added to adjust the pH to 3, further stirring to complete the coupling reaction, filtration, and the following formula ( 27.0 parts of a monoazoamino compound represented by A-61ML) was obtained.
  • Example E9 Synthesis of azo compound of formula (A-92) 11.1 parts of ureido compound represented by the above formula (A-92) was obtained in the same manner as in Example E8 except that 10.7 parts of 2-methylaniline was used instead of 2,5-dimethylaniline. It was. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 435 nm.
  • Example E10 Synthesis of azo compound of formula (A-95) Example E9 except that 16.2 parts of 3- (2-aminophenoxy) propane-1-sulfonic acid were used instead of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid In the same manner as above, 12.7 parts of a ureido compound represented by the above formula (A-95) was obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 428 nm.
  • Example E11 Synthesis of azo compound of formula (A-99) A ureido represented by the above formula (A-99) in the same manner as in Example E9, except that 16.2 parts of 3- (2-aminophenoxy) propane-1-sulfonic acid was used instead of 2-methoxyaniline. 13.5 parts of compound were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 434 nm.
  • Example E12 Synthesis of azo compound of formula (A-100) 11.0 parts of ureido compound represented by the above formula (A-100) was obtained in the same manner as in Example E9, except that 12.1 parts of 2-ethylaniline was used instead of 2-methylaniline. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 435 nm.
  • Example E13 Synthesis of azo compound of formula (B-17) 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, 12.1 parts of 2,5-dimethylaniline was added, and while stirring at 10-30 ° C., sodium carbonate was added to adjust the pH to 3, further stirring to complete the coupling reaction, filtration, and the following formula ( 30.8 parts of a monoazoamino compound represented by B-17ML).
  • Example E14 Synthesis of azo compound of formula (B-1) 12.
  • the maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 427 nm.
  • Example E15 Synthesis of azo compound of formula (B-20) 10.2 parts of a ureido compound represented by the above formula (B-20) in the same manner as in Example E13, except that 13.8 parts of 5-amino-2-chlorobenzoic acid is used in place of 4-aminobenzoic acid. Got. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 432 nm.
  • Example E16 Synthesis of azo compound of formula (B-29)
  • Example E14 except that 18.7 parts of 2-amino-5-methylbenzenesulfonic acid was used instead of 4-aminobenzene-1,3-disulfonic acid, which is a raw material of the disazoamino compound (B-17D).
  • 10.1 parts of a ureido compound represented by the above formula (B-29) were obtained.
  • the maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 425 nm.
  • Example E17 Synthesis of azo compound of formula (B-48) 13.5 parts of a ureido compound represented by the above formula (B-48) was obtained in the same manner as in Example E13, except that 10.7 parts of 2-methylaniline was used instead of 2,5-dimethylaniline.
  • the maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 433 nm.
  • Example E18 Synthesis of azo compound of formula (C-5) Add 30.8 parts of monoazoamino compound (B-17ML) to 400 parts of water, dissolve with sodium hydroxide, add 25.0 parts of 35% hydrochloric acid at 10-30 ° C., and then 5.5 parts of sodium nitrite And stirred at 20-30 ° C. for 1 hour to diazotize. Thereto, 19.6 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid was added, and while stirring at 20-30 ° C., sodium carbonate was added to pH 4, and the mixture was further stirred. The ring reaction was completed and filtered to obtain 41.0 parts of a disazoamino compound represented by the following formula (C-5D).
  • Example E19 Synthesis of azo compound of formula (C-16) 12.
  • the maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 437 nm.
  • Example E20 Synthesis of azo compound of formula (C-19) It is represented by the above formula (C-19) in the same manner as in Example E18 except that 13.8 parts of 5-amino-2-chlorobenzoic acid is used in place of 2-amino-5-methylbenzenesulfonic acid. 13.5 parts of ureido compound were obtained. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 435 nm.
  • Example E21 Synthesis of azo compound of formula (C-46) 10.7 parts of 2-methylaniline instead of 2,5-dimethylaniline, and 3- (2-amino-4-methylphenoxy) propane-1 instead of 2-methoxy-5-methylaniline -13.1 parts of a ureido compound represented by the above formula (C-46) was obtained in the same manner as in Example E19 except that 19.7 parts of sulfonic acid was used. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 440 nm.
  • Example E22 Synthesis of azo compound of formula (C-49) 10.7 parts of 2-methylaniline was used instead of 2,5-dimethylaniline, and 3- (2-amino-4-chlorophenoxy) propane-1- was used instead of 2-methoxy-5-methylaniline Except for using 21.3 parts of sulfonic acid, 13.7 parts of a ureido compound represented by the above formula (C-49) was obtained in the same manner as in Example E19. The maximum absorption wavelength of this compound in a 20% aqueous pyridine solution was 438 nm.
  • Examples F1 to F22 Production of dye-based polarizing film
  • Polyvinyl alcohol having a thickness of 75 ⁇ m was immersed in each aqueous solution (dye bath) at 45 ° C.
  • Table 1 shows the absorption wavelength and the polarization rate when the polarization rate of the obtained dye-based polarizing film is maximized. As shown in Table 1, the polarizing films prepared using the compounds of the present invention all had a high polarization rate.
  • the measurement of the absorption wavelength when the polarization rate of the polarizing film is maximized and the calculation of the polarization rate are performed by using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) for parallel transmission and orthogonal transmission at the time of polarization incidence. Calculated using rate.
  • the parallel transmittance (Ky) is a transmittance measured by setting the absorption axis of an absolute polarizer (polarizing plate having a polarization degree of 99.99%) and the absorption axis of a polarizing film in parallel, and orthogonal transmission.
  • the rate (Kz) indicates the transmittance measured by setting the absorption axis of the absolute polarizer and the absorption axis of the polarizing film orthogonally.
  • the parallel transmittance and orthogonal transmittance at each wavelength were measured at 1 nm intervals at 380 to 780 nm. Using the measured values, the polarization rate at each wavelength was calculated from the following formula (I) to obtain the highest polarization rate at 380 to 780 nm and the absorption wavelength (nm) at that time.
  • Polarization rate (%) [(Ky ⁇ Kz) / (Ky + Kz)] ⁇ 100 (I)
  • Table 2 shows the contrast at the maximum absorption wavelength of the dye-based polarizing films obtained in Examples F1 to F22 and Comparative Examples 1 and 2.
  • the polarization performance was evaluated by preparing samples so that the parallel transmittance at the maximum absorption wavelength of the dye-based polarizing film would be equal. As shown in Table 2, all of the dye-based polarizing films of Examples F1 to F22 had a higher contrast than the dye-based polarizing films of Comparative Examples 1 and 2.
  • Example P1 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P2 Production of neutral gray polarizing plate
  • 0.1% of the compound of the formula (A-20) obtained in Example E4 0.2% of C Eye Direct Red 81, 0.05% of C Eye Direct Blue 274 and 0.
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P3 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance at 380 to 700 nm of 42% and an orthogonal average transmittance of 0.02%, and had a high degree of polarization.
  • a triacetyl cellulose film (TAC film: manufactured by Fuji Film Co., Ltd .: trade name TD-80U) is laminated through an adhesive of the above, and a support provided with an AR layer is pasted using an adhesive, and a TAC / polarizing film A dye-based polarizing plate (neutral gray polarizing plate) in which the / TAC / AR support was laminated in this order was obtained.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • Example P4 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P5 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P6 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P7 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P8 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P9 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P10 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P11 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • Example P12 Production of neutral gray polarizing plate
  • a polarizing film was produced in the same manner as in Example F1 except that a 45 ° C. aqueous solution having a concentration of 1% was used.
  • the obtained polarizing film had a single plate average transmittance of 380 to 700 nm of 42% and an orthogonal transmittance of 0.02%, and had a high degree of polarization.
  • TAC film manufactured by Fuji Film Co., Ltd .: trade name TD-80U
  • TD-80U triacetyl cellulose film
  • the neutral gray polarizing plates obtained in Examples P1 to P12 have no change in the single-plate average transmittance even after 400 hours under the conditions of 80 ° C. and 90% RH, and they last for a long time even at high temperature and high humidity. Shows durability. Further, the neutral gray polarizing plates of Examples P1 to P12 showed no change in single-plate average transmittance even after 200 hours in the xenon light resistance test, and were excellent in light resistance against long-time exposure to light. From these results, it is shown that the neutral gray polarizing plates of Examples P1 to P12 are high-performance dye-based polarizing plates having excellent polarization performance and having moisture resistance, heat resistance, and light resistance. It was done.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

L'objet de la présente invention est de fournir un composé azoïque qui est utile en tant que colorant dichroïque à utiliser dans une plaque polarisante. La présente invention concerne un composé azoïque représenté par la formule (1) ou un sel de celui-ci. (Dans la formule, chacun des A1 et A2 représente, indépendamment l'un de l'autre : un groupe naphtyle qui peut comporter un substituant choisi dans un groupe constitué par un groupe hydroxy, un groupe alcoxy comportant un groupe sulfo et de 1 à 4 atomes de carbone, et un groupe sulfo ; ou un groupe phényle qui peut comporter un substituant choisi parmi ceux-ci. Chacun des R1 à R6 représente, indépendamment les uns des autres : un atome d'hydrogène, un groupe alkyle ayant de 1 à 4 atomes de carbone, un groupe alcoxy ayant de 1 à 4 atomes de carbone, un groupe alcoxy comportant un groupe sulfo et de 1 à 4 atomes de carbone, un groupe carboxy, un groupe hydroxy, un groupe halogène ; ou un groupe acylamino substitué par un alkyle ayant de 1 à 4 atomes de carbone).
PCT/JP2018/012737 2017-03-31 2018-03-28 Composé azoïque ou sel de celui-ci, et film polarisant à base de colorant, plaque polarisante à base de colorant et appareil d'affichage à cristaux liquides contenant celle-ci Ceased WO2018181470A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020197027526A KR20190134615A (ko) 2017-03-31 2018-03-28 아조 화합물 또는 그 염, 그리고 이것을 함유하는 염료계 편광막, 염료계 편광판, 및 액정 표시 장치
JP2019509971A JP7035018B2 (ja) 2017-03-31 2018-03-28 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、及び液晶表示装置
CN201880009570.3A CN110249008B (zh) 2017-03-31 2018-03-28 偶氮化合物或其盐以及含有它们的染料系偏光膜、染料系偏光板及液晶显示装置

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2017069710 2017-03-31
JP2017-069711 2017-03-31
JP2017069709 2017-03-31
JP2017-069710 2017-03-31
JP2017069711 2017-03-31
JP2017-069709 2017-03-31

Publications (1)

Publication Number Publication Date
WO2018181470A1 true WO2018181470A1 (fr) 2018-10-04

Family

ID=63677090

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/012737 Ceased WO2018181470A1 (fr) 2017-03-31 2018-03-28 Composé azoïque ou sel de celui-ci, et film polarisant à base de colorant, plaque polarisante à base de colorant et appareil d'affichage à cristaux liquides contenant celle-ci

Country Status (5)

Country Link
JP (1) JP7035018B2 (fr)
KR (1) KR20190134615A (fr)
CN (1) CN110249008B (fr)
TW (1) TWI734905B (fr)
WO (1) WO2018181470A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021153374A1 (fr) * 2020-01-29 2021-08-05

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021015188A1 (fr) * 2019-07-22 2021-01-28 日本化薬株式会社 Composé azoïque, film polarisant et plaque polarisante le comprenant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001002631A (ja) * 1999-06-22 2001-01-09 Sumitomo Chem Co Ltd ジスアゾ化合物及びそれを含有する染料系偏光膜
JP2009155364A (ja) * 2007-12-25 2009-07-16 Sumitomo Chemical Co Ltd アゾ化合物及び該アゾ化合物を含有する偏光膜
JP2010502806A (ja) * 2006-09-09 2010-01-28 フジフィルム・イメイジング・カラランツ・リミテッド 方法、化合物、インクおよび使用
WO2016186195A1 (fr) * 2015-05-20 2016-11-24 日本化薬株式会社 Composés azoïques, film polariseur de type colorant et plaque de polariseur comprenant ceux-ci

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2519651A (en) * 1945-07-26 1950-08-22 Ciba Ltd Polyazo dyestuffs
JPS60156759A (ja) 1984-01-25 1985-08-16 Nippon Kayaku Co Ltd 水溶性ジスアゾ化合物
JPH0312606Y2 (fr) 1985-04-09 1991-03-25
JP4162334B2 (ja) 1999-07-26 2008-10-08 日本化薬株式会社 染料系偏光膜
JP2001108828A (ja) 1999-10-06 2001-04-20 Sumitomo Chem Co Ltd トリスアゾ化合物を含有する染料系偏光膜
JP4078476B2 (ja) 1999-12-24 2008-04-23 住友化学株式会社 アゾ化合物又はその塩及びそれらを含有する染料系偏光膜
JP5204944B2 (ja) * 2004-06-07 2013-06-05 富士フイルム株式会社 黒インク組成物、およびインクジェット記録方法。
JP2009512737A (ja) * 2005-10-20 2009-03-26 富士フイルム株式会社 インク組成物、インクの製造方法、インクセット、並びに記録方法
JP2009132794A (ja) 2007-11-30 2009-06-18 Nippon Kayaku Co Ltd アゾ化合物、インク組成物、記録方法及び着色体
JP6054588B1 (ja) * 2015-05-20 2016-12-27 日本化薬株式会社 染料系偏光素子、並びにこれを用いた偏光板及び液晶表示装置
TWI715585B (zh) * 2015-05-20 2021-01-11 日商日本化藥股份有限公司 偶氮化合物及含有此等之染料系偏光膜以及偏光板
JP6702622B2 (ja) * 2015-05-20 2020-06-03 日本化薬株式会社 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001002631A (ja) * 1999-06-22 2001-01-09 Sumitomo Chem Co Ltd ジスアゾ化合物及びそれを含有する染料系偏光膜
JP2010502806A (ja) * 2006-09-09 2010-01-28 フジフィルム・イメイジング・カラランツ・リミテッド 方法、化合物、インクおよび使用
JP2009155364A (ja) * 2007-12-25 2009-07-16 Sumitomo Chemical Co Ltd アゾ化合物及び該アゾ化合物を含有する偏光膜
WO2016186195A1 (fr) * 2015-05-20 2016-11-24 日本化薬株式会社 Composés azoïques, film polariseur de type colorant et plaque de polariseur comprenant ceux-ci

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021153374A1 (fr) * 2020-01-29 2021-08-05
WO2021153374A1 (fr) * 2020-01-29 2021-08-05 日本化薬株式会社 Composé azoïque ou sel de celui-ci, et film polarisant à base de colorant, plaque polarisante à base de colorant et appareil d'affichage chacun contenant celu-ci
JP7724160B2 (ja) 2020-01-29 2025-08-15 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

Also Published As

Publication number Publication date
KR20190134615A (ko) 2019-12-04
JPWO2018181470A1 (ja) 2020-02-06
JP7035018B2 (ja) 2022-03-14
TWI734905B (zh) 2021-08-01
CN110249008A (zh) 2019-09-17
TW201843245A (zh) 2018-12-16
CN110249008B (zh) 2021-06-11

Similar Documents

Publication Publication Date Title
JP5296536B2 (ja) アゾ化合物及びその塩並びにそれらを含有する染料系偏光膜
JP5544289B2 (ja) 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
JP5225839B2 (ja) アゾ化合物及びそれらを含有する染料系偏光膜
JP5366819B2 (ja) アゾ化合物及びそれらを含有する染料系偏光膜
JP5899122B2 (ja) アゾ化合物、染料系偏光膜及び偏光板
JP5366947B2 (ja) アゾ化合物及びその塩、並びにそれらを含有する染料系偏光膜並びに偏光板
JP4825135B2 (ja) アゾ化合物およびそれらを含有する染料系偏光膜または偏光板
JP6617098B2 (ja) 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
JP6736549B2 (ja) 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
JP7035018B2 (ja) 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、及び液晶表示装置
JP6702622B2 (ja) 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
JP6824160B2 (ja) 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
JP7724160B2 (ja) 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
HK40008128A (en) Azo compound or salt thereof, and dye-based polarizing film, dye-based polarizing plate, and liquid-crystal display apparatus containing same
HK1243447B (zh) 偶氮化合物和含有偶氮化合物的染料型偏振膜以及偏振板
HK1187940B (en) Azo compound, dye-based polarizing film, and polarizing plate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18775226

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019509971

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20197027526

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18775226

Country of ref document: EP

Kind code of ref document: A1