WO2018135618A1 - Composé azoïque ou sel de celui-ci, et film ainsi que plaque de polarisation à base de colorant comprenant ce composé - Google Patents

Composé azoïque ou sel de celui-ci, et film ainsi que plaque de polarisation à base de colorant comprenant ce composé Download PDF

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Publication number
WO2018135618A1
WO2018135618A1 PCT/JP2018/001588 JP2018001588W WO2018135618A1 WO 2018135618 A1 WO2018135618 A1 WO 2018135618A1 JP 2018001588 W JP2018001588 W JP 2018001588W WO 2018135618 A1 WO2018135618 A1 WO 2018135618A1
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Prior art keywords
group
formula
carbon atoms
dye
polarizing film
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PCT/JP2018/001588
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English (en)
Japanese (ja)
Inventor
貴大 樋下田
典明 望月
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日本化薬株式会社
株式会社ポラテクノ
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Application filed by 日本化薬株式会社, 株式会社ポラテクノ filed Critical 日本化薬株式会社
Priority to CN201880005420.5A priority Critical patent/CN110114418B/zh
Priority to JP2018562447A priority patent/JP7010850B2/ja
Priority to KR1020197019885A priority patent/KR20190103181A/ko
Publication of WO2018135618A1 publication Critical patent/WO2018135618A1/fr

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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
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/28—Disazo or polyazo compounds containing copper
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a novel azo compound or a salt thereof, and a dye-based polarizing film containing them.
  • a polarizing plate having a light transmission / shielding function is used in 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, indoor / outdoor information display devices, measuring devices, and the like. 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. In recent years, not only display applications but also applications for improving accuracy in authenticity determination devices, and applications for improving S / N ratio by cutting reflected light in image sensors such as CCD and CMOS.
  • a general polarizing plate is a polarizing film such as a stretched and oriented film of polyvinyl alcohol or a derivative thereof, or a polyene film obtained by orienting a polyene by dehydrochlorination of a polyvinyl chloride film or dehydration of a polyvinyl alcohol film.
  • the substrate is produced by dyeing or containing iodine or a dichroic dye as a polarizing element.
  • an iodine-based polarizing film using iodine as a polarizing element is excellent in polarization performance, but is weak against water and heat, and is durable when used for a long time at high temperature and high humidity. There's a problem.
  • a dye-type polarizing film using a dichroic dye as a polarizing element is superior in moisture resistance and heat resistance to an iodine-type polarizing film, in general, the polarizing performance is not sufficient.
  • the present invention makes it possible to produce a high-performance polarizing film and polarizing plate that function with respect to light having a wavelength in the infrared region, and a stretched film using a dichroic dye having absorption in the infrared region.
  • An object is to provide an azo compound or a salt thereof.
  • the present inventors have obtained a film containing a dye having an absorption in the infrared region, and the light having an infrared wavelength is formed by the orientation of the dye in the film.
  • the inventors have newly found that a polarizing plate functioning with respect to can be achieved, and have completed the present invention.
  • the present invention relates to the following [1] to [13].
  • R 1 is a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, hydroxy A C 1-4 alkyl group having a group, a C 1-4 alkyl group having a carboxy group, a C 1-4 alkoxy group having a sulfo group, a C 1-4 alkoxy group having a hydroxy group , And a group consisting of an alkoxy group having 1 to 4 carbon atoms having a carboxy group (in the case where there are a plurality of them, each independently), R 2 represents a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms
  • R 3 represents the same as R 1 in formula (2)
  • R 4 and R 5 each independently represents a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a 1 to carbon atom having a sulfo group.
  • R 6 is a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms having a sulfo group
  • An alkyl group having 1 to 4 carbon atoms having a hydroxy group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and 1 to 1 carbon atoms having a hydroxy group Selected from the group consisting of 4 alkoxy groups and a C 1-4 alkoxy group having a carboxy group;
  • x represents an integer of 1 to 3.
  • the azo compound or a salt thereof according to [1] represented by [6] A dye-based polarizing film having absorption in at least the near infrared region, comprising the azo compound or a salt thereof according to any one of [1] to [5] and a polarizing film substrate.
  • 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 [5] and one or more organic dyes other than these.
  • a dye-based polarizing film comprising two or more kinds of the azo compound or a salt thereof according to any one of [1] to [5], one or more organic dyes other than these, and a polarizing film substrate.
  • a liquid crystal display device comprising the dye-based polarizing film according to any one of [6] to [9] or the dye-based polarizing plate according to [10].
  • the dye-based polarizing film according to any one of [6] to [9] which exhibits neutral gray.
  • An on-vehicle display device or an outdoor display device comprising the dye-based polarizing film according to [12] or a dye-based polarizing plate obtained by bonding a transparent protective layer to at least one surface of the dye-based polarizing film.
  • the present invention makes it possible to produce a high-performance polarizing film and polarizing plate that function with respect to light having a wavelength in the infrared region, and a stretched film using a dichroic dye having absorption in the infrared region.
  • An azo compound or a salt thereof can be provided.
  • the polarizing plate according to the present invention is a polarizing plate for light in the infrared wavelength region that can be handled in the same manner as a conventional dye-based polarizing plate.
  • the polarizing plate of the present invention has flexibility and / or physical stability.
  • stray light is not generated because the polarizing plate of the present invention is an absorption type.
  • the polarizing plate of the present invention has high weather resistance (heat resistance, moist heat resistance, light resistance).
  • the azo compound of the present invention has the following formula (1): Or an salt thereof.
  • the two bonds of —NH— are each independently bonded to the substitution position represented by a or b, preferably the substitution position represented by a.
  • a 1 and A 2 are a hydrogen atom or the following formula (2): Or the following formula (3): It is represented by However, the case where both A 1 and A 2 are hydrogen atoms is excluded.
  • One of A 1 and A 2 is a hydrogen atom and the other is represented by formula (2), or both A 1 and A 2 are represented by formula (2).
  • both A 1 and A 2 are represented by formula (2).
  • the ring substituted by R 1 and the sulfo group is a benzothiazole ring when there is no ring represented by a broken line, and naphtho when a ring represented by a broken line is present.
  • Thiazole ring When there is no ring represented by a broken line, that is, when the ring substituted by R 1 is a benzothiazole ring, the substitution positions of R 1 and the sulfo group are not particularly limited, but only the 4-position, only the 6-position, A combination of the 4th and 6th positions and a combination of the 6th and 7th positions are preferable, and a combination of only the 6th position and the 4th and 6th positions is more preferable.
  • the substitution position is not particularly limited, but the combination of the 6th and 8th positions, the 4th and 6th positions, A combination of the 8th position and a combination of the 4th, 7th and 9th positions are preferable, and a combination of the 6th and 8th positions is more preferable.
  • R 1 is a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, hydroxy A C 1-4 alkyl group having a group, a C 1-4 alkyl group having a carboxy group, a C 1-4 alkoxy group having a sulfo group, a C 1-4 alkoxy group having a hydroxy group And a C 1-4 alkoxy group having a carboxy group.
  • a sulfo group and an alkoxy group having 1 to 4 carbon atoms are preferred. When there are a plurality of R 1 , they are each independently selected.
  • the alkoxy group having 1 to 4 carbon atoms having a hydroxy group is preferably a linear alkoxy group in which the end of the alkoxy group is substituted with a hydroxy group, more preferably a 4-hydroxypropoxy group or a 4-hydroxybutoxy group.
  • the alkoxy group having 1 to 4 carbon atoms having a carboxy group is preferably a linear alkoxy group in which the end of the alkoxy group is substituted with a carboxy group, more preferably a 4-carboxypropoxy group or a 4-carboxybutoxy group.
  • the alkoxy group having 1 to 4 carbon atoms having a sulfo group is preferably a linear alkoxy group in which the terminal of the alkoxy group is substituted with a sulfo group, and more preferably a 4-sulfopropoxy group or a 4-sulfobutoxy group.
  • R 2 represents a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, hydroxy A C 1-4 alkyl group having a group, a C 1-4 alkyl group having a carboxy group, a C 1-4 alkoxy group having a sulfo group, a C 1-4 alkoxy group having a hydroxy group And a C 1-4 alkoxy group having a carboxy group.
  • the substitution position is not particularly limited, but the para position of R C is preferred.
  • M represents an integer of 1 to 3.
  • the ring substituted by R 3 is a benzothiazole ring when there is no ring represented by a broken line, and a naphthothiazole ring when a ring represented by a broken line is present. is there.
  • the substitution position of R 3 is not particularly limited, but only 4-position, 6-position only, 4-position The 6-position combination and the 6-position and 7-position combination are preferred, and the 6-position alone and 4-position and 6-position combinations are more preferred.
  • the substitution position is not particularly limited, but the combination of the 6th and 8th positions, the 4th and 6th positions, A combination of the 8th position and a combination of the 4th, 7th and 9th positions are preferable, and a combination of the 6th and 8th positions is more preferable. Only the 2nd position, only the 6th position, only the 7th position, the combination of the 2nd position and the 6th position, and the combination of the 2nd position and the 7th position are preferable, and only the 2nd position and the combination of the 2nd position and the 7th position are particularly preferable.
  • R 3 represents the same meaning as R 1 in formula (2), and is independently selected from R 1 .
  • R 4 and R 5 each independently represents a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a 1 to carbon atom having a sulfo group.
  • alkyl groups having 1 to 4 carbon atoms having a hydroxy group 1 to 4 carbon groups having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and a carbon number having a hydroxy group It is selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms having a carboxy group.
  • a sulfo group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms is preferable.
  • substitution position is not particularly limited, only the 6-position and the 7-position are preferred.
  • N represents an integer of 1 to 3.
  • a 1 is a hydrogen atom
  • R a is a hydroxy group
  • R a together with R c or R d is —O—Cu -O- is formed.
  • a 2 is a hydrogen atom
  • R b is a hydroxy group
  • R b together with R c or R d is —O—Cu -O- is formed.
  • the azo compound represented by the formula (1) is preferably the formula (4): It is represented by In the formula (4), R 6 represents a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a 1 to carbon atom having a sulfo group.
  • alkyl groups having 1 to 4 carbon atoms having a hydroxy group 1 to 4 carbon groups having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and a carbon number having a hydroxy group It is selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms having a carboxy group.
  • x represents an integer of 1 to 3.
  • the azo compound represented by the formula (1) may be in a free form or a salt form.
  • the salt can be, for example, an alkali metal salt such as a lithium salt, a sodium salt, and a potassium salt, or an organic salt such as an ammonium salt or an alkylamine salt.
  • the salt is preferably a sodium salt.
  • the azo compound represented by the formula (1) or a salt thereof is, for example, diazotized according to a normal method for producing an azo dye as described in Dye Chemistry (Toyo Hosoda, 1957, page 621). It can manufacture by performing coupling.
  • the following method is mentioned as an example of a specific manufacturing method.
  • the aminothiazoles represented by the following formula (A) are diazotized and subjected to primary coupling with anilines represented by the following formula (B) or aminonaphthalenes represented by the following formula (C), and the following formula (D Or a monoazoamino compound represented by the following formula (E).
  • Each of the monoazoamino compounds (D) or (E) is diazotized, and secondarily coupled with naphthols of the following formula (F), respectively, and a copper salt is added to the resulting azo compound to form a copper complex.
  • the azo compound (1) is obtained.
  • R 0 and R 0 has the same meaning as explained for R 1 in formula (2) or R 3 in formula (3)
  • R 2 represents The same meaning as in formula (2) is represented
  • R 4 and R 5 represent the same meaning as in formula (3)
  • l represents the same meaning as m in formula (2) or n in formula (3).
  • Rp and Rq are substituents having an oxygen atom as a precursor before copper complex chlorination, and are generally a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.
  • the diazotization step is performed by a conventional method in which a nitrite such as sodium nitrite is mixed with a mineral acid aqueous solution or suspension such as hydrochloric acid or sulfuric acid of the diazo component, or a neutral or weak diazo component. It is preferable to carry out by the reverse method of adding nitrite to an alkaline aqueous solution and mixing this 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 and acetic acid with each of the above diazo solutions and at a temperature of ⁇ 10 to 40 ° C. and a pH of 2 to 7.
  • the monoazo compound of the formula (D) or the formula (E) obtained by coupling is filtered as it is, precipitated by aciding out or salting out and filtered out, or in the next step as a solution or suspension. You can also go to. If the diazonium salt is insoluble and in suspension, it can be filtered and used as a press cake in the next coupling step.
  • the secondary coupling reaction between the diazotized compound of the monoazo compound of formula (D) or formula (E) and the naphthols represented by formula (F) is neutral at a temperature of ⁇ 10 to 40 ° C. and a pH of 7 to 10. It is preferably carried out under alkaline conditions. After completion of the reaction, the obtained azo compound or a salt thereof is preferably precipitated by salting out and filtered out. Further, when purification is necessary, 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.
  • a copper salt such as copper sulfate, copper chloride, and copper acetate is added to the aqueous solution containing the azo compound or salt thereof obtained in the secondary coupling reaction, and ammonia, monoethanolamine, and The reaction is carried out in the presence of amines such as diethanolamine, for example at 70 to 100 ° C.
  • the aminothiazole compound represented by the formula (A) is represented as 2-aminobenzothiazole when there is no ring represented by a broken line, for example, 2-amino-6-sulfobenzothiazole, 2-aminobenzothiazole, Examples include amino-7-methoxy-6-sulfobenzothiazole, 2-amino-4,6-disulfobenzothiazole, and 2-amino-7-methoxy-4,6-disulfobenzothiazole.
  • the aminothiazole compound represented by the formula (A) is represented as 2-aminonaphthothiazole when a ring represented by a broken line is present, for example, 2-amino-6,8-disulfonaphthothiazole.
  • anilines of the formula (B) examples include 2-methoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 2,6-dimethoxyaniline, 2-ethoxyaniline, 2-ethoxy-5- Examples include methylaniline, 2,5-diethoxyaniline, 2,6-diethoxyaniline, 2-methoxy-5-ethoxyaniline, 2-ethoxy-5-methoxyaniline, or 2-methoxy-5-chloroaniline. .
  • Preferred examples include 2-methoxy-5-methylaniline and 2,5-dimethoxyaniline. These anilines may have an amino group protected.
  • aminonaphthalenes of the formula (C) examples include 1-amino-2-methoxynaphthalene-6-sulfonic acid, 1-amino-2-methoxynaphthalene-7-sulfonic acid, 1-amino-2-ethoxynaphthalene- Examples include 6-sulfonic acid and 1-amino-2-ethoxynaphthalene-7-sulfonic acid. Preferred is 1-amino-2-methoxynaphthalene-6-sulfonic acid.
  • the amino group may be protected. Examples of the protecting group include the ⁇ -methanesulfone group.
  • the azo compound or salt thereof according to the present invention has absorption in the near infrared region.
  • the azo compound or a salt thereof according to the present invention can be oriented by dyeing and stretching on a film to exhibit absorption having anisotropy, and is useful as a dye for a polarizing film.
  • the infrared region generally refers to 700 to 30000 nm
  • the near infrared wavelength refers to a wavelength of 700 to 1500 nm.
  • a high-performance dye-based near-infrared absorbing polarizing plate having polarization performance in the near-infrared region can be produced.
  • the azo compound or a salt thereof according to the present invention is a near-red for a neutral gray polarizing plate for vehicle use or outdoor display that is used under a high temperature and high humidity condition, or various sensors that require control of the near infrared region. It is suitable for manufacturing an outer absorption polarizing plate.
  • the dye-based polarizing film includes a dichroic dye containing at least an azo compound represented by the formula (1) or a salt thereof, and a polarizing film substrate, and has absorption in at least the near infrared region.
  • the dye-based polarizing film can be any of a color polarizing film, a neutral gray polarizing film, and a near-infrared absorbing polarizing film, and is preferably a near-infrared absorbing polarizing film.
  • neutral gray is a state in which two polarizing films are overlapped so that their orientation directions are orthogonal to each other (orthogonal position), and in the visible light region and near red region. It means that there is little light leakage (color leakage) of a specific wavelength in the outer region.
  • the dye-based polarizing film may contain one or more azo compounds represented by the formula (1) or a salt thereof as a dichroic dye, and may further contain one or more other organic dyes as necessary. it can.
  • the other organic dye used in combination is not particularly limited, but is 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 has high dichroism. It is preferable. Examples of organic dyes used in combination 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.
  • a representative example is a dye such as Green 59. These dyes are contained in the dye-type polarizing film as free acids or as alkali metal salts (for example, Na salt, K salt, Li salt), ammonium salts, or salts of amines.
  • the target dye-based polarizing film is a near-infrared absorbing polarizing film, a neutral gray polarizing film, a color polarizing film for liquid crystal projectors, or other color polarizing films, respectively.
  • the types of other organic dyes that are made are different.
  • the blending ratio of other organic dyes is not particularly limited, but the total of one or more organic dyes is 0.1 to 10 masses per 100 mass parts of the azo compound of formula (1) or a salt thereof. The range of parts is preferred.
  • the types of other organic dyes used and the blending ratio thereof are adjusted so that the obtained polarizing film has less color leakage in the visible light region and the near infrared wavelength region. Is called.
  • the dye-based polarizing film includes a dichroic dye containing at least the azo compound represented by the formula (1) or a salt thereof, and further containing another organic dye as necessary. ) To be adsorbed and aligned by a known method, mixed with liquid crystal, or aligned by a coating method.
  • the polarizing film substrate is preferably a polymer film, more preferably a film made of polyvinyl alcohol resin or a derivative thereof.
  • Specific examples of the polarizing film substrate include polyvinyl alcohol or derivatives thereof, and any of these 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 or a derivative thereof is preferably used from the viewpoints of dye adsorption and orientation.
  • the thickness of the polarizing film substrate is usually about 30 to 100 ⁇ m, preferably about 50 to 80 ⁇ m.
  • a method of dyeing the polymer film can be usually employed for incorporating the dichroic dye containing at least the azo compound of the formula (1) or a salt thereof.
  • the staining can be performed as follows. First, a dye bath is prepared by dissolving the azo compound of the present invention 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 sodium sulfate at a concentration of about 0.1 to 10% by mass. Dyeing is 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 40 to 80 ° C.
  • the orientation of the dichroic dye containing the azo compound of the formula (1) or a salt thereof is performed by stretching a dyed polymer film.
  • a stretching method any known method such as a wet method or a dry method can 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-treatment is performed for the purpose of improving the light transmittance and the degree of polarization of the dye-based 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 performed, for example, by dipping in a temperature range of 30 to 80 ° C., preferably 40 to 75 ° C., for example, 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 obtained dye-based polarizing film can be used as a polarizing plate by attaching a protective film, and can further be provided with a protective layer or an AR (antireflection) layer and a support, if necessary.
  • Color and neutral gray dye-based polarizing films can be used in, for example, liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation, indoor / outdoor measuring instruments and displays such as cars, and lenses and glasses. Preferably applied.
  • the infrared absorption polarizing film is suitably used for authenticity determination devices, image sensors such as CCD and CMOS, and the like.
  • the dye-based polarizing film has high polarization performance comparable to a polarizing film using iodine, and is excellent in durability.
  • 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.
  • a material for forming the transparent protective film a material excellent in optical transparency and mechanical strength is preferable. For example, in addition to a cellulose acetate film and an acrylic film, a tetrafluoroethylene / hexafluoropropylene copolymer Fluorine films such as polyester film, polyolefin resin or polyamide resin are used.
  • the transparent protective film is preferably a triacetyl cellulose (TAC) film or a cycloolefin film.
  • the thickness of the protective film is usually preferably 40 to 200 ⁇ m.
  • 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 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-based polarizing plate can be used as an elliptically polarizing plate by further attaching a retardation plate to the surface.
  • the dye-based polarizing plate may be any of the above-mentioned near-infrared absorbing polarizing plate, neutral polarizing plate, and color polarizing plate depending on the application.
  • Neutral gray polarizing plate has little color leakage in the orthogonal position in the visible light region and near infrared region, has excellent polarization performance, and prevents discoloration and deterioration of polarization performance even in high temperature and high humidity conditions. This is particularly suitable for in-vehicle use, outdoor display use, security devices that require high reliability, and the like.
  • a neutral gray polarizing plate for in-vehicle use or outdoor display is a polarizing plate with an AR layer provided with an AR layer on a polarizing plate composed of a polarizing film and a protective film in order to further improve the single plate light transmittance.
  • An AR layer provided with a support such as a transparent resin and a polarizing plate with a support 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 on the polarizing plate via an AR layer or directly.
  • the support preferably has a flat portion for attaching a polarizing plate, and since it is used for optical purposes, it is preferably a transparent substrate.
  • 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.
  • Near-infrared absorbing polarizing plates have excellent polarization performance and do not cause discoloration or deterioration of polarization performance even in high-temperature and high-humidity conditions, so they are suitable for use in LCD projectors, in-vehicle, outdoor display, and security devices that require high reliability. Is preferred.
  • These polarizing plates are used by adding a protective film to a dye-based polarizing film to form a polarizing plate, and providing a protective layer or an AR layer and a support as necessary.
  • Single-plate average light transmittance is natural light for a polarizing plate or a single polarizing plate (hereinafter simply referred to as a polarizing plate) that is not provided with a support such as an AR layer and a transparent glass plate. Is the average value of the light transmittance in the specific wavelength region.
  • 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 on two polarizing films or polarizing plates arranged so that the orientation directions are orthogonal.
  • a color polarizing plate with a support for in-vehicle or outdoor display devices is obtained by, for example, applying a transparent adhesive (adhesive) agent on the flat surface of the support, and then applying 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 used here is preferably, for example, an acrylic ester-based one.
  • this dye-type polarizing plate as an elliptically polarizing plate, it is normal to stick a phase difference plate side to a support body side, but you may stick a polarizing plate side to a transparent substrate.
  • a liquid crystal display device includes the dye-based polarizing film or the dye-based polarizing plate.
  • Liquid crystal display devices are used for displays such as calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, and measuring instruments and displays indoors and outdoors, and particularly require high polarization performance and durability. It is suitably used for various liquid crystal displays, for example, for in-vehicle use and outdoor display (for example, display use for industrial instruments and wearable use).
  • the in-vehicle or outdoor liquid crystal display device includes a neutral gray polarizing film or a polarizing plate.
  • Neutral gray polarizing film or polarizing plate has brightness and excellent polarization performance, durability and light resistance, so it is difficult to cause discoloration or deterioration of polarization performance even in high-temperature and high-humidity conditions in the car or outdoors, and is highly reliable for automotive use or An outdoor display device can be realized.
  • Example 1 Add 36.0 parts of 2-aminonaphthothiazole-6,8-disulfonic acid to 100 parts of 98% sulfuric acid, dissolve at 50 ° C., add 12.6 parts of 60% nitric acid, and add 40% at 5-10 ° C. 50 parts of nitrosylsulfuric acid was added dropwise in about 10 minutes and reacted for 1 hour to obtain a diazo reaction liquid. Next, 15.3 parts of 2,5-dimethoxyaniline was dissolved in an acidic aqueous solution obtained by diluting 10.4 parts of 35% hydrochloric acid with 100 parts of water. The diazo reaction liquid was dropped into this aqueous solution over 3 hours and stirred overnight to complete the coupling reaction. Thereafter, filtration was performed to obtain 41.9 parts of a monoazoamino compound represented by the following formula (45).
  • Example 2 Example 1 except that 36.9 parts of 6,6′-iminobis (1-hydroxynaphthalene-3-sulfonic acid) are replaced with 36.9 parts of 7,7′-iminobis (1-hydroxynaphthalene-3-sulfonic acid) In the same manner as above, 53.5 parts of the compound represented by the formula (9) was obtained. The maximum absorption wavelength of the compound in a 20% aqueous pyridine solution was 756 nm.
  • Example 3 In the same manner as in Example 1, except that 36.0 parts of 2-aminonaphthothiazole-6,8-disulfonic acid was replaced with 26.0 parts of 2-amino-7-methoxybenzothiazole-6-sulfonic acid, the compound of the formula (15 ) 46.7 parts of a compound represented by The maximum absorption wavelength of the compound in a 20% aqueous pyridine solution was 692 nm.
  • Example 4 In a solution obtained by diazotizing 41.9 parts of the compound represented by the formula (45) in the same manner as in Example 1, and adding 79.6 parts of the compound represented by the formula (46) to 200 parts of water. The solution was added dropwise while maintaining the pH at 9 to 11, and stirred to complete the coupling reaction. Then, after salting out with sodium chloride, it filtered and 78.4 parts of tetrakisazo compounds represented by Formula (47) were obtained.
  • Example 5 Except that the compound represented by the formula (8) was changed to the compound represented by the formula (9), 66.6 parts of the compound represented by the formula (18) were obtained in the same manner as in Example 4.
  • the maximum absorption wavelength of the compound in a 20% aqueous pyridine solution was 806 nm.
  • Example 6 In the same manner as in Examples 1 and 4, except that 36.0 parts of 2-aminonaphthothiazole-6,8-disulfonic acid was replaced with 23.0 parts of 2-aminobenzothiazole-6-sulfonic acid, a compound represented by the formula (27 ) was obtained 55.9 parts. The maximum absorption wavelength of the compound in a 20% aqueous pyridine solution was 706 nm.
  • Example 7 Example 1 and Example 4 except that 36.0 parts of 2-aminonaphthothiazole-6,8-disulfonic acid was replaced with 26.0 parts of 2-amino-7-methoxybenzothiazole-6-sulfonic acid. , 55.9 parts of a compound represented by the formula (29) were obtained. The maximum absorption wavelength of the compound in a 20% aqueous pyridine solution was 723 nm.
  • Example 8 40.6 parts of a monoazo compound represented by the formula (48) was obtained in the same manner as in Example 1 except that 15.3 parts of 2,5-dimethoxyaniline was replaced with 13.7 parts of 2-methoxy-5-methylaniline. It was.
  • Example 9 It is represented by the formula (13) in the same manner as in Example 1 except that 36.0 parts of 2-aminonaphthothiazole-6,8-disulfonic acid is replaced with 23.0 parts of 2-aminobenzothiazole-6-sulfonic acid. 46.7 parts of The maximum absorption wavelength of the compound in a 20% aqueous pyridine solution was 652 nm.
  • 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 in the range of 380 to 1100 nm. Using the measured values, the polarizability of each wavelength was calculated from the following formula (i), and the maximum polarizability in the range of 380 to 1100 nm and the absorption wavelength (nm) at that time were obtained. The results are shown in Table 1.
  • Polarization rate (%) [(Ky ⁇ Kz) / (Ky + Kz)] ⁇ 100 (i)
  • the transmissivity in the visible light region was almost constant for both parallel and orthogonal positions, and a neutral gray hue was exhibited.
  • One triacetyl cellulose film (TAC film; manufactured by Fuji Photo Film Co., Ltd .; trade name TD-80U) was laminated on both sides of the polarizing film with an adhesive of an aqueous polyvinyl alcohol solution.
  • an AR support (manufactured by NOF Corp .; Realak X4010) was laminated on one TAC film using an adhesive to obtain a neutral gray dye-based polarizing plate with an AR support.
  • the obtained polarizing plate exhibited a neutral gray hue and had a high polarization rate.
  • the obtained polarizing plate showed durability for a long time even in a high temperature and high humidity state, and was excellent in light resistance against long-time exposure.

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

Abstract

L'invention a pour objet de fournir un film ainsi qu'une plaque de polarisation très performants qui tout en consistant en films étirés mettant en œuvre un colorant dichroïque absorbant dans la région de l'infrarouge, agissent sur les rayonnements de longueur d'onde de la région de l'infrarouge. L'invention a également pour objet de fournir un composé azoïque ou un sel de celui-ci permettant la fabrication de ce film et de cette plaque. Plus précisément l'invention fournit un composé azoïque ou un sel de celui-ci représenté par la formule (1) (dans la formule, Ａ１ et Ａ２ représentent chacun indépendamment un atome d'hydrogène ou la formule (2), toutefois, le cas où Ａ１ et Ａ２ sont tous les deux des atomes d'hydrogène est exclu, lorsque Ａ１ est un atome d'hydrogène, alors Ｒａ représente un groupe hydroxy, lorsque Ａ１ est représenté par la formule (2) ou la formule (3), alors Ｒａ forme －Ｏ－Ｃｕ－Ｏ－ avec Ｒｃ ou Ｒｄ, lorsque Ａ２ est un atome d'hydrogène, alors Ｒｂ est un groupe hydroxy, lorsque Ａ２ est représenté par la formule (2) ou la formule (3), alors Ｒｂ forme －Ｏ－Ｃｕ－Ｏ－ avec Ｒｃ ou Ｒｄ).
PCT/JP2018/001588 2017-01-20 2018-01-19 Composé azoïque ou sel de celui-ci, et film ainsi que plaque de polarisation à base de colorant comprenant ce composé WO2018135618A1 (fr)

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CN201880005420.5A CN110114418B (zh) 2017-01-20 2018-01-19 偶氮化合物或其盐、以及含有偶氮化合物或其盐的染料系偏光膜及染料系偏光板
JP2018562447A JP7010850B2 (ja) 2017-01-20 2018-01-19 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及び染料系偏光板
KR1020197019885A KR20190103181A (ko) 2017-01-20 2018-01-19 아조 화합물 또는 그 염, 그리고 이것을 함유하는 염료계 편광막 및 염료계 편광판

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WO2019117123A1 (fr) * 2017-12-13 2019-06-20 日本化薬株式会社 Élément polarisant pour région visible et région infrarouge, et plaque polarisante
JPWO2020203640A1 (fr) * 2019-04-05 2020-10-08
JP2021162736A (ja) * 2020-03-31 2021-10-11 大日本印刷株式会社 機能性フィルム、偏光板及び画像表示装置
JP2021162737A (ja) * 2020-03-31 2021-10-11 大日本印刷株式会社 機能性フィルム、偏光板及び画像表示装置

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WO2019117123A1 (fr) * 2017-12-13 2019-06-20 日本化薬株式会社 Élément polarisant pour région visible et région infrarouge, et plaque polarisante
CN111448494A (zh) * 2017-12-13 2020-07-24 日本化药株式会社 可见光区域及红外线区域用偏光元件及偏光板
JPWO2019117123A1 (ja) * 2017-12-13 2021-01-07 日本化薬株式会社 可視域および赤外域用偏光素子、および、偏光板
CN111448494B (zh) * 2017-12-13 2022-05-31 日本化药株式会社 可见光区域及红外线区域用偏光元件及偏光板
JP2023052132A (ja) * 2017-12-13 2023-04-11 日本化薬株式会社 可視域および赤外域用偏光素子、および、偏光板
JP7319195B2 (ja) 2017-12-13 2023-08-01 日本化薬株式会社 可視域および赤外域用偏光素子、および、偏光板
JPWO2020203640A1 (fr) * 2019-04-05 2020-10-08
WO2020203640A1 (fr) * 2019-04-05 2020-10-08 株式会社ポラテクノ Élément polarisant avec nanofibres de cellulose (cnf) et plaque polarisante
JP2021162736A (ja) * 2020-03-31 2021-10-11 大日本印刷株式会社 機能性フィルム、偏光板及び画像表示装置
JP2021162737A (ja) * 2020-03-31 2021-10-11 大日本印刷株式会社 機能性フィルム、偏光板及び画像表示装置
JP7532858B2 (ja) 2020-03-31 2024-08-14 大日本印刷株式会社 機能性フィルム、偏光板及び画像表示装置

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