Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
  • C09B31/16—Trisazo dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
  • C09B31/30—Other polyazo dyes
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • 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 polarizing film containing a novel azo compound or a salt thereof, a polarizing plate, and a liquid crystal display device.
• a polarizing plate having a light transmission / shielding function is a basic component of a display device (display) such as a liquid crystal display (LCD) together with a liquid crystal having a light switching function.
• display such as a liquid crystal display (LCD) together with a liquid crystal having a light switching function.
• LCD liquid crystal display
• the fields of application 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, indoor and outdoor measuring devices, and the like. It can also be applied to lenses having a polarizing function, and has been applied to sunglasses with improved visibility and, in recent years, polarized glasses compatible with 3D televisions and the like.
• the polarizing plate as described above Since the applications of the polarizing plate as described above are widespread, it is used under a wide range of conditions such as low temperature to high temperature, low humidity to high humidity, and low light to high light, resulting in high polarization performance and high durability. There is a demand for a polarizing plate having properties.
• polarizing plates are formed by dyeing or impregnating a film of polyvinyl alcohol or a derivative thereof with iodine or a dichroic dye and stretching and orienting the film, or by dehydrogenating a polyvinyl chloride film or dehydrating a polyvinyl alcohol-based film. It is manufactured by aligning it.
• iodine-based polarizing film produced by using iodine is excellent in polarizing performance, it is vulnerable to water and heat, and has a problem in its durability when used for a long time in a high temperature and high humidity state.
• the dye-based polarizing film produced by using a dye is superior in moisture resistance and heat resistance to the iodine-based polarizing film, but the polarizing performance is generally not sufficient.
• Dye-based neutral gray polarizing plates are generally manufactured by combining multiple types of dyes, but the polarization performance of dye-based neutral gray polarizing plates is not sufficient, and the two colors with good polarization performance for each color used. It was necessary to develop a sex dye.
• Examples of the dye-based polarizing film as described above include dye-based polarizing films prepared by using the water-soluble azo compounds described in Patent Documents 1 to 3, but still sufficient polarization characteristics can be obtained. Has not been reached, and further improvement in performance has been required.
• Japanese Unexamined Patent Publication No. 05-053014 Japanese Unexamined Patent Publication No. 05-295282 Japanese Unexamined Patent Publication No. 09-230142 Japanese Unexamined Patent Publication No. 11-218611 Japanese Unexamined Patent Publication No. 2001-33627 Japanese Unexamined Patent Publication No. 2009-132794 Japanese Unexamined Patent Publication No. 2001-240762 Japanese Unexamined Patent Publication No. 2001-108828 Japanese Unexamined Patent Publication No. 60-156759
• One of the objects of the present invention is to provide a high-performance polarizing film and a polarizing plate having excellent polarizing performance. Furthermore, another object of the present invention is to provide a neutral gray polarizing plate for color leakage at orthogonal positions in the wavelength region of the visible light region. Still another object of the present invention is to provide a high-performance polarizing plate having excellent polarization performance and durability (heat resistance, moisture resistance or light resistance).
• a polarizing film and a polarizing plate containing a specific azo compound and a salt thereof have excellent polarizing performance and durability.
• a polarizing film containing an azo compound represented by the following formula (1) or a salt thereof (In formula (1), Ra 1 , Ra 2 , Ab 1 , and Ab 2 are substituted with either ring a or ring b, and one of Ra 1 and Ra 2 is a hydroxy group and the other. Represents a hydrogen atom, a hydroxyl group or a C1-4 alkoxy group having a C1-4 alkoxy group or a sulfo group, and any one of Ab 1 and Ab 2 has a sulfo group, a carboxy group, or a substituent.
• the other is a substituent selected from the group consisting of an amino group which may have a hydrogen atom, a sulfo group, a carboxy group or a substituent, and Rb 1 to Rb 6 are independent of each other.
• h is 0 or Representing 1
• Xb 1 has an amino group which may have at least one substituent S, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, and a substituent.
• the substituent S (independently if there is a plurality of groups) is an alkyl of C1 to 4 which may further have a substituent. It is selected from the group consisting of a group, a C1-4 alkoxy group, a sulfo group, an amino group, a C1-4 alkylamino group, a hydroxy group, a carboxy group, and a carboxyethylamino group, and Ra 1 , Ra 2 , and the above. It is different from Ab 1 and Ab 2.
• the polarizing film and the polarizing plate of the present invention have excellent polarizing performance.
• the polarizing plate having a neutral gray color of the present invention exhibits a high-performance achromatic color without color leakage at orthogonal positions in the wavelength region of the visible light region.
• the polarizing film and the polarizing plate of the present invention have excellent polarization performance (transmittance, contrast) and durability (moisture resistance, heat resistance, light resistance).
• azo compound or salt thereof may be simply referred to as "azo compound” unless it clearly represents a free form.
• the "substituent” may contain a hydrogen atom, and therefore the hydrogen atom may be described as a "substituent” for convenience. "May have a substituent” means that a case without a substituent is also included.
• a "phenyl group which may have a substituent” includes an unsubstituted mere phenyl group and a phenyl group having a substituent.
• the "lower” such as the lower alkyl group and the lower alkoxy group of the present application has a carbon atom number of 1 to 4 (C1 to 4), preferably 1 to 3 (C1 to 3). Is shown.
• the polarizing film of the present invention contains an azo compound represented by the following formula (1) or a salt thereof.
• Ra 1 , Ra 2 , Ab 1 , and Ab 2 are substituted with either ring a or ring b, and one of Ra 1 and Ra 2 is a hydroxy group and the other.
• the other is a substituent selected from the group consisting of an amino group which may have a hydrogen atom, a sulfo group, a carboxy group or a substituent, and Rb 1 to Rb 6 are independent of each other.
• Xb 1 has an amino group which may have at least one substituent S, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, and a substituent.
• the substituent S (independently if there is a plurality of groups) is an alkyl of C1 to 4 which may further have a substituent. It is selected from the group consisting of a group, a C1-4 alkoxy group, a sulfo group, an amino group, a C1-4 alkylamino group, a hydroxy group, a carboxy group, and a carboxyethylamino group, and Ra 1 , Ra 2 , and the above. It is different from Ab 1 and Ab 2.
• the amino group which may have a substituent which can be selected as Rb 1 to Rb 6 preferably has one or two unsubstituted amino groups or substituents (alkyl groups and acetyl groups of C1 to 4). It is an amino group.
• the amino group which may have a substituent S is preferably an unsubstituted amino group or a substituent (hydroxy group, methoxy group, ethoxy group, amino group, carboxy group, sulfo group, phenyl group). It is an amino group having one or two good C1-4 alkyl groups, more preferably an amino group having one or two hydrogen atoms and a methyl group.
• the phenylamino group which may have a substituent is preferably one selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, a carboxy group, an amino group, and a lower alkylamino group.
• a phenylamino group having two substituents more preferably one or two substituents selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, a sulfo group, a carboxy group and an amino group. It is a phenylamino group that has.
• the phenylazo group which may have a substituent is preferably selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group of C1 to 4, an alkoxy group of C1 to 4, an amino group, a hydroxy group and a carboxyethylamino group. It is a phenylazo group having 1 to 3 to be treated.
• the benzoylamino group which may have a substituent is preferably a benzoylamino group having one substituent selected from the group consisting of a hydrogen atom, a hydroxy group, an amino group and a carboxyethylamino group.
• the naphthotriazole group which may have a substituent is unsubstituted or preferably has one or two substituents selected from the group consisting of a sulfo group, an amino group and a carboxy group. More preferably, it has one or two sulfo groups as substituents.
• the substitution position of the substituent which the phenylamino group, the phenylazo group and the benzoylamino group may have is not particularly limited, but one of the substituents is for each of the amino group, the azo group or the amide group. It is preferably at the p-position.
• the substitution position of Xb 1 is preferably 6-position or 7-position, and more preferably 6-position, when the position of the hydroxy group of the substituted naphthyl group is 1-position.
• the "alkyl group of C1-4" includes, for example, a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group and an n-butyl group, a sec-butyl group and a tert-butyl group.
• a split-chain alkyl group such as, an unsaturated hydrocarbon group such as a vinyl group, and the like.
• alkoxy group of C1 to 4" in the formula (1) examples include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group and the like.
• the azo compound represented by the formula (1) or a salt thereof is the azo compound represented by the following formula (2) or a salt thereof
• a polarizing film having higher transmittance and higher polarization degree can be provided. Further, it is preferable because the transmittance can be further improved in the parallel position of 550 nm to 700 nm and a polarizing film having a high degree of polarization can be provided.
• the azo compound represented by the formula (1) or a salt thereof is a compound represented by the formula (3) or a salt thereof, and more preferably a compound represented by the formula (4) or a salt thereof.
• Ra 1 , Ra 2 , Ab 1 , Ab 2 , Rb 1 to Rb 6 , h, and Xb 1 have the same meanings as in the formula (1), respectively.
• Ra 1 , Ra 2 , Ab 1 , Ab 2 , Rb 1 to Rb 6 , h, and Xb 1 have the same meanings as those in the formula (1).
• Ra 1 , Ra 2 , Ab 1 , Ab 2 , Rb 1 to Rb 6 , h, and Xb 1 have the same meanings as those in the formula (1).
• Ra 1 , Ab 1 , Rb 1 to Rb 6 , h, and Xb 1 each have the same meaning as the formula (1).
• Ra 1 , Ab 1 , Rb 1 to Rb 6 , h, and Xb 1 have the same meanings as those in the formula (1).
• the azo compound represented by the above formula (1) or a salt thereof can be easily produced by performing known diazotization and coupling according to a usual method for producing an azo dye as described in Non-Patent Document 1.
• the amines represented by the formula (A) are diazotized by a known method as described in Non-Patent Document 1, primaryly coupled with the anilines of the following formula (B), and represented by the following formula (C). To obtain a monoazoamino compound.
• Ra 1 , Ra 2 , Ab 1 , Ab 2 , Rb 1 , and Rb 2 have the same meanings as those in the formula (1).
• this monoazoamino compound (C) is diazotized by a known method as described in Non-Patent Document 1, secondaryly coupled with the anilines of the following formula (D), and represented by the following formula (E). Obtain a disazoamino compound.
• Ra 1 , Ra 2 , Ab 1 , Ab 2 , Rb 1 to Rb 4 have the same meanings as those in the formula (1), respectively.
• the azo compound of the formula (2) can be obtained by diazotizing the formula (E) by a known method as described in Non-Patent Document 1 and coupling it with the naphthols represented by the following formula (F).
• the diazotization step is carried out by the normal method of mixing a mineral acid aqueous solution such as hydrochloric acid or sulfuric acid of the diazo component or a nitrite such as sodium nitrite with a turbid solution, or a neutral or weak alkaline diazo component. This is done by the reverse method of adding nitrite to the aqueous solution and mixing it with mineral acid.
• the temperature of diazotization is preferably ⁇ 10 to 40 ° C.
• the coupling step with anilines is performed by mixing an acidic aqueous solution such as hydrochloric acid or acetic acid with each of the above diazo solutions at a temperature of ⁇ 10 to 40 ° C. and acidic conditions of pH 2 to 7.
• the monoazo compound and disazo compound obtained by coupling can be taken out as they are, or they can be precipitated by acidation or salting out and filtered out, or they can proceed to the next step as a solution or a turbid solution. If the monoazo compound or disazo compound obtained by coupling is a sparingly soluble and turbid liquid, it can be filtered and used as a press cake in the next coupling step.
• the coupling reaction between the diazodized diazo compound and the naphthols represented by the formula (F) is preferably carried out at a temperature of -10 to 40 ° C. under neutral to alkaline conditions of pH 7 to 10. After completion of the reaction, the reaction product is precipitated by salting out, filtered and taken 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 starting material for synthesizing the azo compound represented by the formula (1) or a salt thereof is the substituted naphthylamine compound represented by the formula (A).
• the naphthylamines of the formula (A) include 2-amino-1-hydroxy-naphthalene-6-sulfonic acid, 3-amino-1-hydroxy-naphthalene-6-sulfonic acid, and 2-amino-8-hydroxy-.
• Naphthalene-6-sulfonic acid 3-amino-8-hydroxy-naphthalen-6-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalen-6-sulfonic acid, 3-amino-1,8-dihydroxy-naphthalene -6-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalene-3-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalene-3,6-disulfonic acid, 2-amino-1-methoxy- 8-Hydroxy-naphthalen-6-sulfonic acid, 3-amino-1-methoxy-8-hydroxy-naphthalene-6-sulfonic acid, 2-amino-1-hydroxy-8-methoxy-naphthalen-6-sulfonic acid, 3 -Amino-1-hydroxy-8-methoxy-naphthalen-6-sulfonic acid, 2-amino-1-hydroxy-8- (3-s
• 2-amino-1,8-dihydroxy-naphthalen-6-sulfonic acid 2-amino-1,8-dihydroxy-naphthalene-3-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalen-3, 6-Disulfonic acid, 2-amino-1-methoxy-8-hydroxy-naphthalene-6-sulfonic acid, 2-amino-1-hydroxy-8-methoxy-naphthalene-6-sulfonic acid.
• anilines 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, 3- (2-amino-4-methyl) Phenoxy) Propane-1-
• examples of naphthols having Xb 1 which is a tertiary coupling component when h is 0 or a quaternary coupling component when h is 1, are 6-amino-3.
• the azo compound represented by the above formula (1) or a salt thereof are given below.
• the azo compound is represented in the form of a free acid.
• the azo compound represented by the formula (1) may be in the form of a free acid or a salt, respectively, or may be a salt of a metal ion or an ammonium ion.
• the metal ion include alkali metal ions such as lithium ion, sodium and potassium ion, and alkaline earth metal ions such as calcium ion and magnesium ion.
• ammonium ion examples include ammonium ion, methylammonium ion, dimethylammonium ion, triethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, triethanolammonium ion and the like. .. More specifically, for example, in the case of free acid, sulfonic acid (-SO 3 H), in the case of sodium ion, sodium sulfonate (-SO 3 Na), in the case of ammonium ion, ammonium sulfonate (-SO). 3 NH 4 ) is represented.
• the polarizing film of the present invention contains an azo compound represented by the formula (1) or a salt thereof as a dichroic dye.
• the polarizing film may be a neutral gray polarizing film or a color polarizing film, and is preferably a neutral gray polarizing film.
• neutral gray is 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"), and is specified in the wavelength region of the visible light region. It means that there is little light leakage (color leakage) of the wavelength.
• the polarizing film of the present invention contains an azo compound represented by the formula (1) or a salt thereof as a dichroic dye, either alone or in a combination of a plurality of types, and is represented by the formula (1), if necessary.
• One or more organic dyes other than the azo compound can be further contained.
• the other organic dye is not particularly limited, but 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 is used. preferable.
• Other organic dyes include, for example, C.I. Ai. direct. Yellow 12, Sea. Ai. direct. Yellow 28, Sea. Ai. direct. Yellow 44, Sea. Ai. direct. Orange 26, Sea. Ai. direct. Orange 39, Sea.
• Non-Patent Document 2 Ai. direct. Orange 71, Sea. Ai. direct. Orange 107, Sea. Ai. direct. Red 2, Sea. Ai. direct. Red 31, Sea. Ai. direct. Red 79, Sea. Ai. direct. Red 81, Sea. Ai. direct. Red 247, Sea. Ai. direct. Green 80 and Sea. Ai. direct. Green 59 and the dyes described in Non-Patent Document 2 are typical examples, but it is preferable to use dyes developed for polarizing plates as described in Patent Documents 4 to 9 depending on the purpose. .. These organic dyes are used as free acids, alkali metal salts (eg Na salt, K salt, Li salt), ammonium salts, or salts of amines.
• alkali metal salts eg Na salt, K salt, Li salt
• the type of organic dye to be blended differs depending on the target polarizing film, which is a neutral gray polarizing film, a color polarizing film for liquid crystal projectors, and other color polarizing films.
• the blending ratio is not particularly limited, but in general, the total of at least one or more of other organic dyes 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 about 100 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass.
• the types and blending ratios of other organic dyes used in combination are adjusted so as to reduce color leakage in the wavelength region of the visible light region of the obtained polarizing film. ..
• the target polarizing film When the target polarizing film is a color polarizing film, for example, it has a high single plate average light transmittance in a specific wavelength range of the obtained polarizing film and a low average light transmittance at an orthogonal position, for example, a specific one.
• the types and blending ratios 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 range and an orthogonal average light transmittance of 0.4% or less. ..
• the polarizing film of the present invention is a dichroic dye containing an azo compound represented by the formula (1) or a salt thereof, and if necessary, another dye, which is also referred to as a polarizing film base material (simply, "base material"). It can be produced by containing it in a known method and orienting it.
• the base material is preferably a polymer film, and more preferably a film made of a polyvinyl alcohol resin or a derivative thereof.
• the base material include polyvinyl alcohol resins or those modified with olefins such as ethylene and propylene, unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, and maleic acid. ..
• a film made of a polyvinyl alcohol resin or a derivative thereof is preferably used from the viewpoint of dye adsorptivity and orientation.
• the thickness of the base material is usually about 10 to 100 ⁇ m, preferably about 20 to 80 ⁇ m.
• a method of dyeing the polymer film is usually adopted to contain the azo compound of the formula (1) or a salt thereof.
• the dyeing is performed, for example, as follows. First, a dyeing bath is prepared by dissolving the azo compound represented by the formula (1) or a salt thereof, and if necessary, other organic dyes in water.
• the dye concentration in the dyeing bath is not particularly limited, but is usually selected from the range of about 0.001 to 10% by mass. Further, a dyeing aid may be used if necessary, and for example, it is preferable to use Glauber's salt at a concentration of, for example, about 0.1 to 10% by mass.
• the polymer film can be immersed in the dyeing bath thus prepared for, for example, 1 to 10 minutes for dyeing.
• 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 9 times, preferably 3 to 8 times, and more preferably 4 to 7 times.
• any known method such as a wet method or a dry method may be used.
• the polymer film may be stretched before dyeing.
• the orientation of the water-soluble dye is performed at the time of dyeing.
• the polymer film containing and oriented the water-soluble dye is subjected to post-treatment such as boric acid treatment by a known method, if necessary. Such post-treatment is performed for the purpose of improving the light transmittance and the degree of polarization of the polarizing film.
• the conditions for boric acid treatment vary depending on the type of polymer film used and the type of dye used, but in general, the boric acid concentration of the boric acid aqueous solution is, for example, 0.1 to 15% by mass, preferably 1 to 10%.
• the treatment temperature is in the range of% by mass, the treatment temperature is 30 to 80 ° C., preferably 40 to 75 ° C., and the film is immersed for 0.5 to 10 minutes.
• an aqueous solution containing a cationic polymer compound may be used in combination with a fixing treatment.
• polarizing film of the present invention include, for example, liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments and displays, lenses, glasses and the like.
• the polarizing film produced by using the dye of the present invention (hereinafter, also referred to as “dye-based polarizing film”) is a polarizing film produced by using iodine (hereinafter, also referred to as “iodine-based polarizing film”). It has comparable high polarization performance and is also excellent in durability. Therefore, it is particularly suitable for various liquid crystal displays and liquid crystal projectors that require high polarization performance and durability, for example, for in-vehicle and outdoor displays (for example, display applications of industrial instruments and wearable applications). be.
• the polarizing plate of the present invention (hereinafter, also referred to as "dye-based polarizing plate”) can be obtained by laminating a transparent protective film on one side or both sides of a polarizing film.
• the polarizing plate of the present invention has excellent polarization performance and durability (moisture resistance, heat resistance, light resistance).
• a material having excellent optical transparency and mechanical strength is preferable, and for example, a cellulose acetate film, an acrylic film, an ethylene tetrafluoride / propylene hexafluoride copolymer and the like are used.
• the transparent protective film is preferably a triacetyl cellulose (TAC) film or a cycloolefin-based film.
• TAC triacetyl cellulose
• the thickness of the protective film is usually preferably 40 to 200 ⁇ m.
• An adhesive can be used to bond the polarizing film and the protective film of the present invention.
• the adhesive examples include polyvinyl alcohol-based adhesives, urethane emulsion-based adhesives, acrylic-based adhesives, polyester-isocyanate-based adhesives, and the like, and polyvinyl alcohol-based adhesives are suitable.
• a transparent protective layer may be further provided on the surface of the polarizing plate of the present invention.
• the transparent protective layer include an acrylic-based or polysiloxane-based hard coat layer and a urethane-based protective layer.
• an antireflection layer AR layer
• the AR layer can be formed by depositing or sputtering a substance such as silicon dioxide or titanium oxide, or by applying a thin coat of a fluorine-based substance.
• the dye-based polarizing plate preferably further includes a support.
• the dye-based polarizing plate can also be used as an elliptical polarizing plate by attaching a retardation plate to the surface.
• the polarizing plate of the present invention may be either a neutral gray polarizing plate or a color polarizing plate depending on the intended use.
• the neutral gray polarizing plate of the present invention has a neutral color, has less color leakage at orthogonal positions in the polarization region of the visible light region, has excellent polarization performance, and suppresses discoloration and deterioration of polarization performance even in a high temperature and high humidity state. It is suitable for in-vehicle or outdoor display because of its high durability.
• an AR layer is provided on the polarizing plate composed of the polarizing film and the transparent protective film of the present invention in order to further improve the single light transmittance, and the polarizing plate with the AR layer is provided.
• It is preferably a plate, and more preferably an AR layer to which both an AR layer and a support such as a transparent resin are attached and a polarizing plate with a support.
• 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, may be provided directly on the polarizing plate, or may be provided with a polarizing plate with an AR layer (AR layer / polarizing plate / AR layer) on the support. ..
• the AR layer and the polarizing plate with a support preferably include an AR layer / a polarizing plate / an AR layer / a support in this order.
• the support preferably has a flat surface portion for attaching the polarizing plate, and is preferably a transparent substrate because it is used for optics.
• Transparent substrates are broadly divided into inorganic substrates and organic substrates.
• Inorganic substrates such as soda glass, borosilicate glass, crystal substrates, sapphire substrates, and spinel substrates, as well as acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and Examples thereof include an organic substrate such as a cycloolefin polymer, but an organic substrate is preferable.
• the thickness and size of the transparent substrate may be a desired size.
• the color polarizing plate has excellent polarization performance and does not cause discoloration or deterioration of polarization performance even in high temperature and high humidity conditions, and is therefore suitable for liquid crystal projectors and display devices for in-vehicle and outdoor displays.
• the color polarizing plate for a liquid crystal projector has brightness and excellent polarization performance, and the required wavelength range of the polarizing plate (A. When an ultrahigh pressure mercury lamp is used; 420 to 500 nm for a blue channel and 500 to 500 for a green channel).
• the average light transmission rate at the orthogonal position is 0.4% or less, more preferably the average light transmission rate of the single plate in the required wavelength range of the polarizing plate is 41% or more, and the average light transmission rate at the orthogonal position is 0. It is 0.3% or less, more preferably 0.2% or less. More preferably, the average light transmittance of the single plate in the required wavelength range of the polarizing plate is 42% or more, and the average light transmittance at the orthogonal position is 0.1% or less.
• the average light transmittance of a single plate is a specific wavelength region when natural light is incident on a single polarizing plate (hereinafter, also simply referred to as “polarizing plate”) without 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 the average value of the light transmittance in a specific wavelength region when natural light is incident on the two polarizing plates 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, an AR layer, a support, or the like, if necessary, in the dye-based polarizing plate. good.
• the color polarizing plate with a support can be obtained, for example, by applying a transparent adhesive (adhesive) agent to the flat surface portion of the support and then attaching a dye-based polarizing plate to the coated surface.
• a transparent adhesive (adhesive) may be applied to the dye-based polarizing plate, and then a support may be attached to the coated surface.
• the adhesive for example, an acrylic acid ester-based adhesive is preferable.
• the retardation plate side is usually attached to the support in the order of stacking the dye-based polarizing plate / retardation plate / support.
• the polarizing plate side may be attached to the support to form a stacking order of the retardation plate / polarizing plate / support.
• the display device of the present invention includes the polarizing film or the polarizing plate of the present invention.
• the display device include a liquid crystal display device or an organic electronics display device, for example, for a calculator, a clock, a notebook computer, a word processor, a liquid crystal television, a car navigation system, and a display such as an indoor / outdoor measuring instrument or a display device.
• a display such as an indoor / outdoor measuring instrument or a display device.
• it is suitably used for various display bodies that require high polarization performance and durability, for example, for in-vehicle or outdoor displays (for example, display applications and wearable applications of industrial instruments).
• the dye-based polarizing film or the dye-based polarizing plate provided in the display device is preferably neutral gray.
• a dye-based polarizing plate is arranged on either or both of the incident side and the exit side of the liquid crystal cell.
• the dye-based polarizing plate may or may not be in contact with the liquid crystal cell, but from the viewpoint of durability, it is preferable that the dye-based polarizing plate is not in contact with the liquid crystal cell.
• 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.
• the dye-based polarizing plate is arranged on both the incident side and the exit side of the liquid crystal cell, and further, the polarizing plate surface of the dye-based polarizing plate is placed on the liquid crystal cell side and the support surface is provided. It is preferable to arrange it on the light source side.
• the incident side of the liquid crystal cell is the light source side, and the opposite side is called the exit side.
• the liquid crystal cell provided in the liquid crystal display device is, for example, an active matrix type, and is formed by enclosing a liquid crystal between a transparent substrate on which an electrode and a TFT are formed and a transparent substrate on which a counter electrode is formed. Is preferable.
• a light source such as a cold cathode fluorescent lamp or a white LED passes through a dye-based polarizing plate, then passes through a liquid crystal cell, a color filter, and a dye-based polarizing plate, and is projected onto a display screen.
• the liquid crystal display device Since the dye-based polarizing plate has brightness, excellent polarization performance, polarization and light resistance, the liquid crystal display device is less likely to cause discoloration or deterioration of polarization performance even in high temperature and high humidity conditions such as inside or outdoors, and is reliable. high.
• Example S1 (Step 1) After adding 15.0 parts of commercially available N-acetyl-1,4-phenylenediamine to 200 parts of water and stirring, 42 parts of 35% hydrochloric acid and 17.3 parts of 40% sodium nitrite were added for 1 hour. Diazotization was performed by stirring. Next, 32.0 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid was added to 200 parts of water and dissolved in a 25% aqueous sodium hydroxide solution as weakly alkaline. The previously obtained diazo solution was added dropwise to this solution at a pH of 6.5 to 8.0, and the mixture was stirred to complete the coupling reaction.
• reaction solution was stirred at 90 to 99 ° C. for 5 hours at a pH of 0.5 or less (for example, 0.01 to 0.5) to carry out a hydrolysis reaction, and then the precipitated solid was filtered off. 150 parts of a wet cake of the monoazo compound represented by the formula (7) was obtained.
• Step 2 150 parts of the obtained wet cake of the monoazo compound represented by the formula (7) was added to 300 parts of water, stirred and suspended, and the pH was adjusted to 9.0 using 25% sodium hydroxide, and 40% sodium nitrite was added thereto. 17.3 parts of aqueous solution was added. The obtained aqueous solution was added dropwise to a mixed solution of 200 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo solution. 15.3 parts of 2,5-dimethoxyaniline was added to the obtained diazo solution, and the mixture was stirred with 15% sodium carbonate aqueous solution at pH 1.5 to 4.0 for 8 hours to complete the coupling reaction. Then, it was salted out with sodium chloride and then filtered to obtain 200 parts of a wet cake of the disuazo compound represented by the formula (8).
• Step 3 200 parts of the obtained wet cake of the disuazo compound represented by the formula (8) was added to 500 parts of water, stirred and suspended, and used with 25% sodium hydroxide to adjust the pH to 9.0, and there was a 40% aqueous sodium nitrite solution. 17.3 parts were added.
• the obtained suspension was added dropwise to a mixed solution of 100 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo solution.
• 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid was added to 300 parts of water and dissolved in a 25% aqueous sodium hydroxide solution as weakly alkaline.
• Example S2 Replace 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid in step 3 of Example S1 with 34.5 parts of 1-hydroxy-6- (4-methoxyphenylamino) -3-naphthalene sulfonic acid. In the same manner as in Example S1 except for the above, 8.0 parts of the azo compound shown in Compound Example 1-10 was obtained.
• Example S3 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid in step 3 of Example S1 and 37.5 parts of 1-hydroxy-6- (2,4-dimethoxyphenylamino) -3-naphthalene sulfonic acid 8.9 parts of the azo compound shown in Compound Example 1-14 was obtained in the same manner as in Example S1 except that it was replaced with.
• Example S4 Replace 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid in step 3 of Example S1 with 35.8 parts of 1-hydroxy-6- (4-aminobenzoylamino) -3-naphthalene sulfonic acid. Except for the above, 11.0 parts of the azo compound shown in Compound Example 1-31 was obtained in the same manner as in Example S1.
• Example S5 (Step 1) 150 parts of the wet cake of the monoazo compound represented by the formula (7) in step 1 of Example S1 was added to 300 parts of water, stirred and suspended, and the pH was adjusted to 9.0 using 25% sodium hydroxide, and 40% thereof. 17.3 parts of an aqueous sodium nitrite solution was added. The obtained aqueous solution was added dropwise to a mixed solution of 200 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo solution. 10.7 parts of 3-methylaniline was added to the obtained diazo solution, and the mixture was stirred with 15% sodium carbonate aqueous solution at pH 1.5 to 4.0 for 8 hours to complete the coupling reaction. Then, it was salted out with sodium chloride and then filtered to obtain 200 parts of a wet cake of the disuazo compound represented by the formula (9).
• Step 2 150 parts of the obtained wet cake of the monoazo compound represented by the formula (9) was added to 300 parts of water, stirred and suspended, and the pH was adjusted to 9.0 using 25% sodium hydroxide, and a 40% aqueous sodium nitrite solution was added thereto. 17.3 parts were added.
• the obtained aqueous solution was added dropwise to a mixed solution of 200 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo solution. 13.7 parts of 2-methoxy-5-methylaniline was added to the obtained diazo solution, and the mixture was stirred with a 15% aqueous sodium carbonate solution at pH 1.5 to 4.0 for 8 hours to complete the coupling reaction. Then, it was salted out with sodium chloride and then filtered to obtain 200 parts of a wet cake of the trisazo compound represented by the formula (10).
• Step 3 200 parts of the obtained wet cake of the trisazo compound represented by the formula (10) was added to 500 parts of water, stirred and suspended, and used with 25% sodium hydroxide to adjust the pH to 9.0, and there was a 40% sodium nitrite aqueous solution 17 . Add 3 parts. The obtained suspension was added dropwise to a mixed solution of 100 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo solution. Next, 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid was added to 300 parts of water and dissolved in a 25% aqueous sodium hydroxide solution as weakly alkaline.
• Example S6 10.7 parts of 3-methylaniline in step 1 of Example S5 is replaced with 12.1 parts of 2,5-dimethylaniline, and 13.7 parts of 2-methoxy-5-methylaniline in step 2 of Example S5 is replaced with 2 parts.
• 5-Dimethoxyaniline 11.0 parts of the azo compound shown in Compound Example 1-42 was obtained in the same manner as in Example S5 except that it was replaced with 15.3 parts.
• Example S7 32.0 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid in step 1 of Example S1 was added to 44.2 parts of 1-hydroxy-3- (3-sulfopropoxy) naphthalene-3,6-disulfonic acid. 12.0 parts of the azo compound shown in Compound Example 1-22 was obtained in the same manner as in Example S1 except that the mixture was replaced.
• Example S1 replaces 32.0 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid in step 1 of Example S1 with 33.4 parts of 1-hydroxy-8-methoxynaphthalene-3,6-disulfonic acid.
• step 3 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid was replaced with 37.5 parts of 1-hydroxy-6- (2,4-dimethoxyphenylamino) -3-naphthalene sulfonic acid. Except for the above, 12.0 parts of the azo compound shown in Compound Example 1-15 was obtained in the same manner as in Example S1.
• Example S9 Same as Example S1 except that 32.0 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid in step 1 of Example S1 was replaced with 22.4 parts of 1-hydroxy-5-naphthalene sulfonic acid. , 12.5 parts of the azo compound shown in Compound Example 1-38 was obtained.
• Example S10 Same as Example S1 except that 32.0 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid in step 1 of Example S1 was replaced with 22.4 parts of 1-hydroxy-3-naphthalenesulfonic acid. , 12.5 parts of the azo compound shown in Compound Example 1-18 was obtained.
• Example S11 Same as Example S1 except that 32.0 parts of 1,8-dihydroxynaphthalene-3,8-disulfonic acid in step 1 of Example S1 was replaced with 30.4 parts of 1-hydroxynaphthalene-3,8-disulfonic acid. Then, 13.5 parts shown in Compound Example 1-19 was obtained.
• Example S12 Examples except that 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid in step 3 of Example S1 was replaced with 25.3 parts of 1-hydroxy-6-methylamino-3-naphthalene sulfonic acid. In the same manner as in S1, 9.2 parts of the azo compound shown in Compound Example 1-36 was obtained.
• Example S13 The compound in the same manner as in Example S1 except that 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid in step 3 of Example S1 was replaced with 34.4 parts of the compound represented by the following formula (11). 11.3 parts of the azo compound shown in Example 1-32 was obtained.
• Example S14 The compound in the same manner as in Example S1 except that 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid in step 3 of Example S1 was replaced with 55.1 parts of the compound represented by the following formula (12). 6.2 parts of the azo compound shown in Example 1-35 were obtained.
• Example S15 Same as Example S1 except that 32.0 parts of 1,8-dihydroxynaphthalene-3,8-disulfonic acid in step 1 of Example S1 was replaced with 30.4 parts of 1-hydroxynaphthalene-3,6-disulfonic acid. Then, 13.5 parts of the azo compound shown in Compound Example 1-7 was obtained.
• Example S16 15.0 parts of N-acetyl-1,4-phenylenediamine in step 1 of Example S1 was replaced with 19.4 parts of N-acetyl-2-methyl-5-methoxy-1,4-phenylenediamine, and Example S1 In step 2, 15.3 parts of 2,5-dimethoxyaniline was replaced with 12.1 parts of 2,5-dimethylaniline, and 1-hydroxy-6-anilino-3-naphthalenesulfonic acid in step 3 of Example S1 was replaced with 31.
• the azo compound 10 shown in Compound Example 1-48 is the same as in Example S1 except that 5 parts are replaced with 1-hydroxy-6- (4-methoxyphenylamino) -3-naphthalenesulfonic acid 34.5 parts. Obtained 0.0 copies
• Example S17 Replaced 15.3 parts of 2,5-dimethoxyaniline in step 2 of Example S1 with 12.1 parts of 2,5-dimethylaniline, and 1-hydroxy-6-anilino-3-naphthalene sulfonate of step 3 of Example S1. It is shown in Compound Example 1-49 in the same manner as in Example S1 except that 31.5 parts of the acid was replaced with 34.5 parts of 1-hydroxy-6- (4-methoxyphenylamino) -3-naphthalene sulfonic acid. 10.0 parts of the azo compound was obtained.
• Example S18 Examples except that 31.5 parts of 1-hydroxy-6-anilino-3-naphthalene sulfonic acid in step 3 of Example S1 was replaced with 32.9 parts of 1-hydroxy-6-benzylamino-3-naphthalene sulfonic acid. In the same manner as in S1, 6.0 parts of the azo compound shown in Compound Example 1-34 was obtained.
• Step 1 15.0 parts of N-acetyl-1,4-phenylenediamine available as a commercially available product is added to 200 parts of water and stirred, then 42 parts of 35% hydrochloric acid and 17.3 parts of 40% sodium nitrite are added and stirred for 1 hour. Diazotized by doing. 22.3 parts of 1-amino-7-naphthalene sulfonic acid was added to the obtained diazo solution, and the mixture was kept at pH 3.5-6.0 with a 15% aqueous sodium carbonate solution and stirred for 8 hours to complete the coupling reaction. .. Then, it was salted out with sodium chloride and then filtered to obtain 100 parts of a wet cake of the monoazo compound represented by the formula (13).
• Step 2 100 parts of the obtained wet cake of the monoazo compound represented by the formula (13) was added to 300 parts of water, stirred and suspended, and the pH was adjusted to 9.0 using 25% sodium hydroxide, and a 40% aqueous sodium nitrite solution was added thereto. 17.3 parts were added.
• the obtained aqueous solution was added dropwise to a mixed solution of 200 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo solution.
• 32.0 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid was added to 200 parts of water and dissolved in a 25% aqueous sodium hydroxide solution as weakly alkaline.
• Examples F1 to F18 and Comparative Examples F1 to F3 Preparation of polarizing film
• Polyvinyl alcohol having a thickness of 75 ⁇ m was added to an aqueous solution (dyeing bath) at 45 ° C. having a concentration of 0.03% of each azo compound and 0.1% of Glauber's salt obtained in Examples S1 to S18 and Comparative Examples S1 to S3. Soaked for minutes.
• This film was stretched 5 times at 50 ° C. in a 3% aqueous boric acid solution, washed with water and dried while maintaining a tense state to obtain a polarizing film.
• Table 1 shows the transmittance and polarization rate of the obtained polarizing film at the maximum absorption wavelength.
• the transmittance and the polarization rate of the maximum absorption wavelength of the polarizing film were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.).
• the simple transmittance (Ts) indicates the transmittance of the maximum absorption wavelength obtained by measuring the polarizing film alone, and the parallel transmittance (Tp) is obtained by measuring and measuring two polarizing films in parallel.
• the transmittance of the maximum absorption wavelength obtained is shown, and the orthogonal transmittance (Tc) indicates the transmittance of the maximum absorption wavelength obtained by measuring and measuring two polarizing films in parallel, and the transmittance ( ⁇ ).
• Is a value calculated by the formula (I)
• the contrast (CR) is calculated by dividing the parallel transmittance by the orthogonal transmittance.
• Example P1 Preparation of neutral gray polarizing plate
• the compound of Compound Example 1-8 obtained in Example S1 was added to 0.3%, C.I. Ai. direct. Red 81 0.15%, Sea. Ai. direct.
• a polarizing film was prepared in the same manner as in Example F1 except that an aqueous solution at 45 ° C. having a concentration of orange 39 at 0.1% and sodium sulfate 0.1% was used as a dyeing bath.
• the single plate average transmittance of the obtained polarizing film at 430 to 640 nm was 42%, and the average transmittance at the orthogonal position was 0.1%, which had a high degree of polarization.
• a triacetyl cellulose film (TAC film: manufactured by Fujifilm Co., Ltd .: trade name TD-80U) is laminated on both sides of this polarizing film via an adhesive of an aqueous polyvinyl alcohol solution, and glass is attached using an adhesive to TAC.
• a dye-based polarizing plate neutral gray polarizing plate in which / polarizing film / TAC / glass was laminated in this order was obtained.
• the neutral gray polarizing plate obtained in Example P1 has no change in the average transmittance of the veneer even after 500 hours in an environment of 105 ° C. and at 80 ° C. at a relative humidity of 90%, and is high in temperature and high. It showed durability over a long period of time even in a damp condition. Further, the neutral gray polarizing plate of Example P1 had no change in the average transmittance of a single plate even after 200 hours had passed under the conditions of 60 W and an environmental temperature of 50 ° C. in a xenon light resistance test (SX-75 manufactured by Suga Test Instruments Co., Ltd.). The light resistance to long-term exposure to light was also excellent. From these results, the neutral gray polarizing plate of Example P1 is a high-performance dye-based polarizing plate having excellent polarization performance and durability (moisture resistance, heat resistance, light resistance). It has been shown.
• the polarizing film of the present invention or the polarizing plate thereof is provided with a protective layer or a functional layer and a transparent support such as glass, crystal, or sapphire, if necessary, and is provided with a liquid crystal projector, a calculator, a clock, a notebook computer, a word processor, a liquid crystal television. , Polarized lenses, polarized glasses, car navigation systems, and indoor / outdoor measuring instruments and displays.
• the polarizing film or the polarizing plate of the present invention can be suitably used for a liquid crystal display device, for example, a reflective liquid crystal display device, a transflective liquid crystal display device, and an organic electroluminescence device other than the liquid crystal display device.

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