CN108603039A - Azo-compound, polarization elements and polarizer and display equipment using the azo-compound - Google Patents

Abstract

Polarization elements and polarizer of the present invention offer with excellent polarization performance and comparison, the display equipment with excellent comparison and the novel azo-compound that can be used in polarization elements and polarizer and display equipment.Azo-compound indicated with the following general formula (1) (in formula, Ab₁Indicate the phenyl with substituent group or the naphthalene with substituent group, Rb₁To Rb₅Independently indicate hydrogen atom, the alkyl of carbon number 1 to 4, the alkoxy of carbon number 1 to 4, sulfonic group or the alkoxy with sulfonic carbon number 1 to 4, Xb₁Indicate can be with substituent group amino, can be with substituent group phenyl amino, can be with substituent group benzoyl-amido, can be with substituent group phenylazo or can be with the aphthotriazoles base of substituent group).Polarization elements and polarizer contain base material and aforementioned azo-compound.Display equipment has aforementioned polarization elements or polarizer.

Description

Azo compound, polarizing component and polarizing plate using the azo compound, and display equipment

technical field

The invention relates to a novel azo compound, a polarizing component and a polarizing plate with a high degree of polarization using the azo compound, and a display device.

Background technique

Polarizers are usually produced by directional adsorption of iodine or dichroic dyes, which are dichroic pigments, on a polyvinyl alcohol resin film. A polarizing plate can be formed by bonding a protective film made of triacetyl cellulose or the like to at least one side of the polarizing unit via an adhesive layer. Polarizing plates can be used in display devices and the like. A polarizing plate using iodine as a dichroic dye is called an iodine-based polarizing plate, while a polarizing plate using a dichroic dye as a dichroic dye is called a dye-based polarizing plate. Among these, dye-based polarizing plates are characterized by high heat resistance, high humidity and heat durability, and high stability, and high color selectivity due to the preparation of dichroic dyes.

In Patent Documents 1 to 4 and Non-Patent Documents 1 and 2, dye-based polarizers containing an azo compound are disclosed.

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 11-218611

Patent Document 2: Japanese Patent No. 4162334

Patent Document 3: Japanese Patent No. 4360100

Patent Document 4: Japanese Patent Laid-Open No. 2004-075719.

non-patent literature

Non-Patent Document 1: Toyoto Hosoda, "Chemistry of Dye", Jihodo Publishing Co., Ltd., 1957, page 621

Non-Patent Document 2: Supervised by Masahiro Irie, "Application of Functional Pigments" (1st Edition), CMC Publishing Co., Ltd., June 2002, pages 98-104.

Contents of the invention

(Problem to be solved by the invention)

However, the conventional polarizers containing azo compounds described in Patent Documents 1 to 4 and Non-Patent Documents 1 and 2 have poor polarizing performance and contrast, and cannot fully respond to the orientation requirements of high-precision displays in recent years.

One of the objectives of the present invention is to provide a polarizing component and a polarizing plate with excellent polarizing performance and contrast, a display device with excellent contrast, and a novel azo compound that can be used in the polarizing component, polarizing plate and display device.

(How to solve the problem)

As a result of intensive studies to solve the aforementioned problems, the inventors of the present invention have found that a novel azo compound can be used as a dichroic dye constituting a polarizing element and a polarizing plate, and have also found that excellent polarization can be achieved by using the azo compound. The present invention is achieved by a polarizing assembly and a polarizing plate with performance and comparison, and a display device with excellent contrast.

That is, the present invention is concerned with the following:

(1) An azo compound represented by the following general formula (1) or a salt thereof.

(In the formula, Ab ₁ represents a phenyl group with a substituent or a naphthyl group with a substituent, Rb ₁ to Rb ₅ independently represent a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons , a sulfonic acid group, or an alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, Xb ₁ represents an amino group that may have a substituent, a phenylamino group that may have a substituent, a benzoylamino group that may have a substituent, A phenylazo group that may have a substituent, or a naphthotriazolyl group that may have a substituent);

(2) An azo compound which is the azo compound described in (1) and is an azo compound represented by the following general formula (2) or a salt thereof.

(wherein, Ab ₁ represents a phenyl group having one or two substituents selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkyl group with 1 to 4 carbons, and an alkoxy group with 1 to 4 carbons, Or a naphthyl group having 2 or 3 substituents selected from the group consisting of a sulfonic acid group, a hydroxyl group, and an alkoxy group with 1 to 4 carbon atoms having a sulfonic acid group; Rb ₁ to Rb ₅ independently represent a hydrogen atom , an alkyl group with 1 to 4 carbons, an alkoxy group _with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons with a sulfonic acid group; The phenylamino group of one or two substituents in the group consisting of an acid group, an amino group and an alkylamino group with 1 to 4 carbon atoms may have one selected from the group consisting of a hydroxyl group, an amino group and a carboxyethylamino group. The benzoylamino group of the substituent may have 1 to 3 substituents selected from the group consisting of hydroxyl, alkyl with 1 to 4 carbons, alkoxy with 1 to 4 carbons, amino and carboxyethylamino phenylazo group, or naphthotriazolyl substituted by 1 or 2 sulfonic acid groups);

(3) An azo compound, which is the azo compound described in (1) or (2), wherein _Xb in the aforementioned general formula (1) or (2) can have a compound selected from methyl, methoxy phenylamino group with one or two substituents in the group consisting of group, sulfonic acid group, amino group and alkylamino group with 1 to 4 carbons;

(4) A polarizing component comprising a substrate and the azo compound described in any one of (1) to (3);

(5) A polarizing component, which is the polarizing component described in (4), and further contains an azo compound represented by the following general formula (3) or a salt thereof,

(In the formula, Ar ₁ represents a phenyl group with a substituent or a naphthyl group with a substituent, Rr ₁ to Rr ₆ independently represent a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons or an alkoxy group with 1 to 4 carbon atoms having a sulfonic acid group, Xr ₁ represents an amino group that may have a substituent, a phenylamino group that may have a substituent, a benzoylamino group that may have a substituent, or a benzoylamino group that may have a substituent phenylazo or naphthotriazolyl which may have substituents, m and n independently represent 0 or 1);

(6) A polarizing component, which is the polarizing component described in (4) or (5), and further contains an azo compound represented by the following general formula (4) or a salt thereof,

(wherein, Ay ₁ represents a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkyl group with a carbon number of 1 to 4, or an alkoxy group with a carbon number of 1 to 4, and Ry ₁ to Ry ₄ independently represent a hydrogen atom, a sulfonic acid group, a carbon An alkyl group with a number of 1 to 4 or an alkoxy group with a number of carbons of 1 to 4, p represents an integer from 1 to 3);

(7) A polarizing component, which is the polarizing component described in (5), wherein the azo compound represented by the aforementioned general formula (3) or a salt thereof is an azo compound represented by the following general formula (5) or a salt thereof ,

(wherein, Ar ₁ represents a phenyl group having one or two substituents selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkyl group with 1 to 4 carbons, and an alkoxy group with 1 to 4 carbons, Or a naphthyl group having 2 or 3 substituents selected from the group consisting of sulfonic acid group, hydroxyl group and alkoxy group with sulfonic acid group having 1 to 4 carbons; Rr ₁ to Rr ₆ independently represent a hydrogen atom , an alkyl group with a carbon number of 1 to 4, an alkoxy group with a carbon number of 1 to ₄ , or an alkoxy group with a carbon number of 1 to 4 with a sulfonic acid group; The phenylamino group of one or two substituents in the group consisting of an acid group, an amino group, and an alkylamino group with 1 to 4 carbon atoms may have 1 A benzoylamino substituent may have 1 to 3 substitutions selected from the group consisting of hydroxyl, alkyl with 1 to 4 carbons, alkoxy with 1 to 4 carbons, amino and carboxyethylamino phenylazo group, or naphthotriazolyl substituted by 1 or 2 sulfonic acid groups; m and n independently represent 0 or 1);

(8) A polarizing component, which is the polarizing component described in (5) or (7), wherein, among the Rr ₅ and Rr ₆ in the aforementioned general formula (3) or (5), one is carbon number 1 to 4 Alkoxy, the other is an alkyl group with 1 to 4 carbons or an alkoxy group with 1 to 4 carbons;

(9) A polarizing component, which is the polarizing component described in (5) or (7), wherein _Xr in the aforementioned general formula (3) or (5) can have a compound selected from methyl, methoxy, A phenylamino group with one or two substituents in the group consisting of a sulfonic acid group, an amino group, and an alkylamino group with 1 to 4 carbon atoms, or may have a phenylamino group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyethylamino group 1 benzoylamino substituent;

(10) A polarizing component, which is the polarizing component described in (6), wherein Ay in the general formula (4) is a carboxyl _group or a sulfonic acid group;

(11) A polarizing component, which is the polarizing component according to any one of (4) to (10), wherein the substrate is a film formed of polyvinyl alcohol or a derivative thereof;

(12) A polarizing plate, equipped with the polarizing component described in any one of (4) to (11), and a transparent protective layer provided on at least one side of the aforementioned polarizing component;

(13) A display device comprising the polarizing element described in any one of (4) to (11), or the polarizing plate described in (12).

(effect of invention)

According to the present invention, it is possible to provide polarizers and polarizers with excellent polarizing properties and contrast, display devices with excellent contrast, and novel azo compounds that can be used in polarizers, polarizers, and display devices.

Detailed ways

Hereinafter, the present invention will be described in detail.

[Novel Azo Compounds]

The azo compound of the present invention is an azo compound represented by the following general formula (1) or a salt thereof. The azo compound of the present invention is a water-soluble dye that functions as a pigment generally called a dichroic dye.

In the general formula (1), Ab ₁ represents a phenyl group with a substituent or a naphthyl group with a substituent, and Rb ₁ to Rb ₅ independently represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, and an alkyl group with 1 to 4 carbon atoms. An alkoxy group or an alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, Xb ₁ represents an amino group that may have a substituent (excluding phenyl and benzoyl), a phenylamino group that may have a substituent, a substituent A benzoylamino group, a phenylazo group which may have a substituent, or a naphthotriazolyl group which may have a substituent.

The azo compound represented by the aforementioned general formula (1) is preferably an azo compound represented by the following general formula (2). Thereby, the polarizing performance of the polarizing device using the azo compound represented by the general formula (1) can be further improved.

(In the formula, Ab ₁ , Rb ₁ to Rb ₅ and Xb ₁ represent the same meanings as in the general formula (1))

Ab ₁ in the aforementioned general formula (1) or (2) represents a substituted phenyl group or a substituted naphthyl group, but may have an alkyl group selected from a sulfonic acid group, a carboxyl group, and a carbon number of 1 to 4 and a phenyl group with one or two substituents in the group consisting of an alkoxy group with a carbon number of 1 to 4, or an alkoxy group with a carbon number of 1 to 4 selected from a sulfonic acid group, a hydroxyl group, and a sulfonic acid group The naphthyl group with 2 or 3 substituents is preferred.

When Ab ₁ in the aforementioned general formula (1) or (2) is a phenyl group having a substituent, it preferably has at least one sulfonic acid group or carboxyl group as the substituent. When Ab ₁ is a phenyl group having two or more substituents, among these substituents, at least one (partial) substituent is a sulfonic acid group or a carboxyl group, and the other substituents are a sulfonic acid group, a carboxyl group, or a carbon number of 1 An alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons having a sulfonic acid group, a nitro group, an amino group, an acetylamino group or an alkylamino group with 1 to 4 carbons is preferred. The substituent on the phenyl group is more preferably a sulfonic acid group, an alkyl group with a carbon number of 1 to 4, an alkoxy group with a carbon number of 1 to 4, a nitro group, an amino group or a carboxyl group, and a sulfonic acid group, a methyl group, a methyl group Oxy, ethoxy or carboxyl are especially preferred. The number of substituents on the phenyl group is preferably 2. The substitution position of the substituent on the phenyl group is not particularly limited, but when the number of substituents on the phenyl group is two, a combination of the 2-position and the 4-position is preferable.

When Ab ₁ in the aforementioned general formula (1) or (2) is a naphthyl group having a substituent, it preferably has at least one sulfonic acid group as the substituent. When Ab ₁ is a naphthyl group having two or more substituents, among these substituents, at least one (partial) substituent is a sulfonic acid group, and the other substituents are a sulfonic acid group, a hydroxyl group, a carboxyl group, or a sulfonic acid group. An alkoxy group having 1 to 4 carbon atoms in the acid group is preferable. When the number of substituents on the naphthyl group is 2, the combination of the substitution positions of these substituents is preferably the combination of the 4-position and the 8-position or the combination of the 6-position and the 8-position, and the combination of the 6-position and the 8-position is preferred. The combination of bit and 8-bit is especially preferred. When the number of substituents on the naphthyl group is three, the combination of the substitution positions of these substituents is particularly preferably a combination of 1-position, 3-position, and 6-position.

As a substituent on the phenyl group or naphthyl group in Ab ₁ , the alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group is preferably a straight chain alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group . In the alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, the substitution position of the sulfonic acid group is preferably at the end of the alkoxy group. As an alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, 3-sulfopropoxy or 4-sulfobutoxy is more preferable, and 3-sulfopropoxy is particularly preferable.

Xb ₁ in the general formula (1) or (2) represents an amino group which may have a substituent (excluding phenyl and benzoyl), a phenylamino group which may have a substituent, and a benzoylamino group which may have a substituent , a phenylazo group that may have a substituent, or a naphthotriazolyl group that may have a substituent; but preferably: may have a group selected from methyl, methoxy, sulfonic acid, amino, and carbon number 1 to 4 The phenylamino group with one or two substituents in the group consisting of alkylamino groups may have a benzoylamino group with one substituent selected from the group consisting of hydroxyl, amino and carboxyethylamino groups, and may have optional A phenylazo group with 1 to 3 substituents from the group consisting of hydroxyl, alkyl with 1 to 4 carbons, alkoxy with 1 to 4 carbons, amino and carboxyethylamino, or through 1 or naphthotriazolyl substituted by 2 sulfonic acid groups; more preferably: may have one selected from the group consisting of methyl, methoxy, sulfonic acid, amino and alkylamino with 1 to 4 carbons Or phenylamino with 2 substituents, or benzoylamino with 1 substituent selected from the group consisting of hydroxyl, amino and carboxyethylamino; more preferably: can have benzoylamino selected from methyl, methyl A phenylamino group having one or two substituents from the group consisting of an oxy group, a sulfonic acid group, an amino group, and an alkylamino group having 1 to 4 carbon atoms. The substitution position of the substituent is not particularly limited, but when Xb ₁ is a phenylamino group having one substituent, a benzoylamino group having one substituent, or a phenylazo group having one substituent , especially preferred in the para position.

Rb ₁ to Rb ₅ in the general formula (1) or (2) independently represent a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, or a carbon number with a sulfonic acid group 1 to 4 alkoxy, preferably a hydrogen atom, an alkyl group with 1 to 4 carbons or an alkoxy group with 1 to 4 carbons, and more preferably a hydrogen atom, methyl or methoxy. And in order to improve the optical properties, the combination of the substitution position of Rb ₁ and Rb ₂ and the combination of the substitution position of Rb ₃ and Rb ₄ are respectively independently the combination of 2-position and 6-position, 2-position and 5-position A combination or a combination of 3-position and 5-position is preferable, and a combination of 2-position and 5-position is more preferable. The substitution position of Rb ₅ is preferably 2-position or 3-position, more preferably 2-position. When the combination of the substitution positions of Rb ₁ and Rb ₂ and the combination of the substitution positions of Rb ₃ and Rb ₄ are independently independent and at least one is a methoxy group, the combination of 2-position and 6-position, 2-position and 5-position A combination of positions or a combination of 3-position and 5-position is preferred, and a combination of 2-position and 5-position is more preferred.

The method for producing the azo compound represented by the aforementioned general formula (1) will be described below. The azo compound represented by the aforementioned general formula (1) can be produced by the same production method as a known production method, so the production method of the azo compound represented by the aforementioned general formula (1) is not limited to the one described here. Manufacturing method. For example, the azo compound represented by the aforementioned general formula (1) can be easily produced by performing well-known diazotization and coupling according to the general azo dye production method described in Non-Patent Document 1.

The azo compound represented by the aforementioned general formula (1) can be produced as follows. First, a monoazoamino compound represented by the following general formula (6) is obtained.

(In the formula, Ab ₁ , Rb ₁ and Rb ₂ represent the same meanings as in the aforementioned general formulas (1) and (2))

For the monoazoamino compound represented by the aforementioned general formula (6), when Ab ₁ is a phenyl group having at least one sulfonic acid group, known aromatic amines represented by the following general formula (7) can be used. Methods Diazotization of sulfoalkoxyaniline acids obtained by sulfoalkylation, and coupling with anilines represented by the following general formula (8) once.

(In the formula, one of Rb ₁₁ and Rb ₁₂ represents a sulfonic acid group or a carboxyl group, and the other represents a sulfonic acid group, a carboxyl group, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a sulfonic acid group alkoxy, carboxyl, nitro, amino, acetylamino, or alkylamino with 1 to 4 carbons)

(In the formula, Rb ₁ and Rb ₂ represent the same meaning as in the aforementioned general formulas (1) and (2))

For the monoazoamino compound represented by the aforementioned general formula (6), when Ab ₁ is a naphthyl group having at least one sulfonic acid group, it can be obtained by combining the naphthylamine sulfonic acids represented by the following general formula (9) or Aminonaphthol sulfonic acids are diazotized with sulfoalkoxynaphthylamine sulfonic acids obtained by sulfonic acid alkylation by a known method, and then reacted once with anilines represented by the aforementioned general formula (8). derived from coupling.

(wherein, Rb ₁₃ represents a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a tosylated hydroxyl group, an amino group, a substituted amino group, a nitro group, a substituted amido group, or a carbon number of 1 to 4 with a sulfonic acid group Alkoxy, q represents an integer from 1 to 3)

Next, diazotize the monoazo amino compound represented by the aforementioned general formula (6) and couple it twice with the aniline represented by the following general formula (10) to obtain the bis-azoamino compound represented by the following general formula (11). Azo amino compounds.

(In the formula, Rb ₃ and Rb ₄ represent the same meaning as in the aforementioned general formula (1) and general formula (2))

(In the formula, Ab ₁ , Rb ₁ , Rb ₂ , Rb ₃ , and Rb ₄ represent the same meanings as in the aforementioned general formula (1) and general formula (2))

Next, diazotize the bis-azoamino compound represented by the general formula (11) to couple with the anilines represented by the following general formula (12) three times to obtain the following general formula (13) Trisazo amino compounds.

(In the formula, Ab ₁ and Rb ₁ to Rb ₅ represent the same meanings as in general formulas (1) and (2))

Next, the trisazo amino compound represented by the aforementioned general formula (13) is diazotized using a well-known method, and it is coupled with naphthols represented by the following general formula (14) 4 times to obtain the following general formula ( 15) The tetrasazo compound represented.

(In the formula, _Xb1 represents the same meaning as in the aforementioned general formulas (1) and (2))

(In the formula, Ab ₁ , Rb ₁ to Rb ₅ and Xb ₁ represent the same meanings as in the aforementioned general formulas (1) and (2))

In the tetraazo compound represented by the aforementioned general formula (15), add copper sulfate and a copper complex salt compound formed by at least one selected from the group consisting of ammonia water, amino alcohol and hexamethylenetetramine, and It is preferable to carry out the copperization reaction at 85° C. to 95° C., whereby a copper complexed azo compound represented by the general formula (1) or (2) is obtained.

The diazotization step in the above-mentioned synthesis can be carried out by mixing sodium nitrite and other nitrites in the diazo component hydrochloric acid, sulfuric acid and other mineral acid aqueous solutions or suspensions, or by adding the diazo component in advance. Add nitrite to neutral or weakly alkaline aqueous solution, and mix this with mineral acid in reverse. The temperature for diazotization is preferably -10 to 40°C. In addition, the coupling step of diazides and anilines is to mix acidic aqueous solutions such as hydrochloric acid and acetic acid with the above-mentioned diazonium solutions (aqueous solutions or suspensions of diazides) at a temperature of -10 to 40°C and a pH of 2 to 7 under acidic conditions.

The monoazoamino compound, bisazoamino compound and trisazoamino compound obtained by coupling can be taken out directly or by acid precipitation or salting out, and then filtered out, and can also be maintained in solution or suspension directly Go to the next step. When the diazonium salt is poorly soluble and forms a suspension, it can also be filtered to form a press cake and used in the next coupling step.

The diazo compound of the trisazo amino compound represented by the general formula (13) and the naphthols represented by the general formula (14) react four times, at a temperature of -10 to 40° C. and a pH of 7 to 10 from neutral to under alkaline conditions. After the reaction is completed, it is taken out by salting out and filtering. In addition, if purification is required, it is only necessary to repeat salting out or use an organic solvent to make it precipitate from water. Examples of the organic solvent used for the purification include alcohols such as methanol and ethanol; and water-soluble organic solvents such as ketones such as acetone.

The aromatic amines represented by the general formula (7) are starting materials (raw material compounds) for synthesizing the azo compounds represented by the aforementioned general formula (1) when Ab ₁ is a phenyl group having a substituent, wherein the general formula ( 7) Rb ₁₁ and Rb ₁₂ of the aromatic amines represented include a hydrogen atom, a sulfonic acid group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group having An alkoxy group having 1 to 4 carbon atoms of an acid group, a naphthotriazolyl group substituted with a sulfonic acid group, a nitro group, an amino group, an acetylamino group or an alkylamino group having 1 to 4 carbon atoms. Rb ₁₁ and Rb ₁₂ are preferably independently hydrogen atoms, sulfonic acid groups, carboxyl groups, alkyl groups with 1 to 4 carbons, or alkoxy groups with 1 to 4 carbons, and at least 1 of Rb ₁₁ and Rb ₁₂ It is more preferable that one is a sulfonic acid group, and it is more preferable that the number of substituents of Rb ₁₁ and Rb ₁₂ is 2 (that is, both Rb ₁₁ and Rb ₁₂ are not hydrogen atoms). The alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group is preferably a straight-chain alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group. Among the alkoxy groups having 1 to 4 carbon atoms having a sulfonic acid group, the substitution position of the sulfonic acid group is preferably at the end of the alkoxy group. As an alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, 3-sulfopropoxy or 4-sulfobutoxy is more preferable.

The aromatic amines represented by general formula (7) include, for example: 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, Benzenesulfonic acid, 2-amino-5-methoxybenzenesulfonic acid, 4-amino-2-methylbenzenesulfonic acid, 3-amino-4-methoxybenzenesulfonic acid, 2-amino-4-sulfonic acid Acid-based benzoic acid, 2-amino-5-sulfonic acid benzoic acid, etc., 5-aminoisophthalic acid, 2-amino-5-nitrobenzenesulfonic acid, 5-acetamide-2-aminobenzenesulfonic acid, 2-amino-5-(3-sulfopropoxy)benzenesulfonic acid, 4-aminobenzene-1,3-disulfonic acid, 2-aminobenzene-1,4-disulfonic acid, etc., and 4 -Aminobenzenesulfonic acid, 2-amino-5-methoxybenzenesulfonic acid, 4-amino-2-methylbenzenesulfonic acid, 4-aminobenzene-1,3-disulfonic acid are especially preferred. In addition, the aromatic amines represented by the general formula (7) may have a naphthotriazolyl group as a substituent on the phenyl group. The aforementioned naphthotriazolyl group includes 6,8-disulfonic acid naphthotriazolyl, 7,9-disulfonic acid naphthotriazolyl, 7-sulfonic acid naphthotriazolyl, 5 - Sulfonic acid naphthotriazolyl and the like. In this case, the naphthotriazolyl group is particularly preferably at the para position of the phenyl group.

The naphthylaminesulfonic acids represented by the aforementioned general formula (9) are starting materials (raw material compounds) for synthesizing the azo compounds represented by the aforementioned general formula (1) when Ab ₁ is a substituted naphthyl group, wherein the aforementioned Rb ₁₃ of the naphthyl amine sulfonic acids represented by general formula (9) is a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a tosylated hydroxyl group, an amino group, a substituted amino group, a nitro group, a substituted amido group or a sulfonic acid group. An alkoxy group having 1 to 4 carbon atoms of an acid group, preferably a hydrogen atom, a sulfonic acid group, or an alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group. In addition, Rb ₁₃ is preferably a hydrogen atom, a hydroxyl group, a carboxyl group, or a lower alkoxy group having a sulfonic acid group. The alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group is preferably a straight-chain alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group. In the alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, the substitution position of the sulfonic acid group is preferably at the end of the alkoxy group. The alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group is preferably 3-sulfopropoxy or 4-sulfobutoxy. In the naphthylamine sulfonic acids represented by the aforementioned general formula (9), the substitution position of the sulfonic acid group can be on any benzene nucleus of the naphthalene ring. When the number q of the sulfonic acid group is 1, the substitution position of the sulfonic acid group is preferably any one of the 1-position, 3-position and 6-position. When the number q of the sulfonic acid group is 2 or 3 , The combination of substitution positions of the sulfonic acid group is preferably a combination of 2 or 3 positions selected from the group consisting of 1-position, 3-position, 6-position and 7-position.

Naphthylaminesulfonic acids represented by the aforementioned general formula (9) include, for example, 2-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 3-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 3-amino-7-nitronaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1 ,6-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 2-aminonaphthalene -1,5-disulfonic acid, 4-aminonaphthalene-1,6-disulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 7-aminonaphthalene-1,3,5-trisulfonic acid Acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 5-aminonaphthalene-1,3,6-trisulfonic acid, 7-amino-3-(3-sulfopropoxy)naphthalene- 1-sulfonic acid, 7-amino-3-(4-sulfobutoxy)naphthalene-1-sulfonic acid, 7-amino-4-(3-sulfopropoxy)naphthalene-2-sulfonic acid , 7-amino-4-(4-sulfobutoxy)naphthalene-2-sulfonic acid, 6-amino-4-(3-sulfopropoxy)naphthalene-2-sulfonic acid, 6-amino -4-(4-sulfobutoxy)naphthalene-2-sulfonic acid, 2-amino-5-(3-sulfopropoxy)naphthalene-1,7-disulfonic acid, 6-amino- 4-(3-sulfopropoxy)naphthalene-2,7-disulfonic acid or 7-amino-3-(3-sulfopropoxy)naphthalene-1,5-disulfonic acid, etc., but With 7-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 7-aminonaphthalene-4-(3 -sulfopropoxy)naphthalene-2-sulfonic acid, 6-amino-4-(3-sulfopropoxy)naphthalene-2-sulfonic acid are preferred, and 7-aminonaphthalene-1,3 -disulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 7-amino-4-(3-sulfopropoxy)naphthalene-2-sulfonic acid are especially preferred.

_Rb 1 and Rb 2 possessed by the anilines represented by the aforementioned general formula (8) which are primary coupling components, and Rb ₃ and Rb ₄ possessed by the anilines represented by the aforementioned general formula (10) which are secondary coupling components, _although each independently represent a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons or an alkoxy group with 1 to 4 carbons having a sulfonic acid group, but preferably a hydrogen atom, methyl, methyl Oxy group or 3-sulfopropoxy group, 4-sulfobutoxy group, more preferably hydrogen atom, methyl group, methoxy group. The combination of the substitution positions of Rb ₁ and Rb ₂ and the combination of the substitution positions of Rb ₃ and Rb ₄ are independently and relative to the combination of the 2-position and the 6-position, the combination of the 2-position and the 5-position, Or the combination of 3-position and 5-position is preferable, and the combination of 2-position and 5-position is more preferable. Examples of anilines having an alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group that can be used as the anilines represented by the aforementioned general formula (8) and the aforementioned anilines represented by the aforementioned general formula (10) include 3-( 2-amino-4-methylphenoxy)propane-1-sulfonic acid, 3-(2-aminophenoxy)propane-1-sulfonic acid, 3-(2-amino-4-methylphenoxy ) butane-1-sulfonic acid, etc. The anilines other than the above that can be used as the anilines represented by the aforementioned general formula (8) and the aforementioned anilines represented by the aforementioned general formula (10) include, for example, 2,5-dimethylaniline, 2,5-diethylaniline, phenylaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5-dimethylaniline, 2,6-dimethylaniline or 3,5-dimethoxyaniline Aniline, etc. These anilines may be anilines in which the amino group is protected by a protecting group. Examples of the aforementioned protecting group include the ω-methanesulfonic acid group thereof. The anilines represented by the aforementioned general formula (8) used in the primary coupling and the anilines represented by the aforementioned general formula (10) used in the secondary coupling may be the same or different.

The anilines having a methoxy group represented by the aforementioned general formula (12) belonging to the tertiary coupling component, as long as they are anilines having a methoxy group in the ortho position relative to the amino group, but the 2,5-dimethoxy Aniline, 2-methoxyaniline, 2-methoxy-5-methylaniline are preferred.

The substituent Xb ₁ of the naphthols represented by the aforementioned general formula (14) belonging to the quaternary coupling component represents an amino group that may have a substituent (excluding phenyl and benzoyl), an amino group that may have a substituent, a phenylamino group that may have a substituent, A benzoylamino group that may have a substituent, a phenylazo group that may have a substituent, or a naphthotriazolyl group that may have a substituent; but preferably: may have a group selected from methyl, methoxy, sulfonic acid, A phenylamino group consisting of one or two substituents of an amino group and an alkylamino group having 1 to 4 carbon atoms may have one substituent selected from the group consisting of a hydroxyl group, an amino group, and a carboxyethylamino group Benzoylamino, phenyl which may have 1 to 3 substituents selected from the group consisting of hydroxyl, alkyl with 1 to 4 carbons, alkoxy with 1 to 4 carbons, amino and carboxyethylamino Azo group, or naphthotriazolyl substituted by 1 or 2 sulfonic acid groups; more preferably: it can have an alkyl group selected from methyl, methoxy, sulfonic acid group, amino group and carbon number 1 to 4 A phenylamino group with one or two substituents in the group consisting of amino groups, or a benzoylamino group with one substituent selected from the group consisting of hydroxyl, amino and carboxyethylamino groups; more preferably: A phenylamino group which may have one or two substituents selected from the group consisting of a methyl group, a methoxy group, a sulfonic acid group, an amino group, and an alkylamino group having 1 to 4 carbon atoms. When _Xb1 is a phenylamino group with one substituent, a benzoylamino group with one substituent, or a phenylazo group with one substituent, the substitution position of the substituent is not particularly limited, but Xb When ₁ is a phenylamino group having one substituent, a benzoylamino group having one substituent, or a phenylazo group having one substituent, the para position is particularly preferable.

The azo compound of the present invention can exist in the form of a free acid represented by the aforementioned general formula (1) or a form of a salt thereof. Examples of the above-mentioned salts include alkali metal salts, alkaline earth metal salts, alkylamine salts, alkanolamine salts, ammonium salts and the like. The above-mentioned salts are preferably sodium salts, potassium salts, or ammonium salts when they are used for dyeing a substrate for polarizing elements. The azo compound represented by the general formula (1) can be isolated in the form of free acid by adding mineral acid after the coupling reaction, and the azo compound represented by the isolated general formula (1) can be separated with water or acidified By washing with water, the inorganic salt can be removed from the isolated azo compound represented by the general formula (1). In this way, the azo compound represented by the general formula (1) in the acid form having a low salt content can be obtained. Next, the acid form of the azo compound represented by the general formula (1) can be neutralized with a desired inorganic or organic base in an aqueous solvent to form a solution of the corresponding salt. Or when salting out after the coupling reaction, the azo compound represented by the general formula (1) can be made into a sodium salt using, for example, sodium chloride, or the azo compound represented by the general formula (1) can be made into a sodium salt using, for example, potassium chloride Make potassium salt. In this way, the azo compound represented by the general formula (1) can be made into a desired salt.

Specific examples of the azo compound or its salt represented by the general formula (1) or (2) of the present invention are given below. In addition, compound examples are shown in the form of free acids.

(Compound Example 1)

(Compound Example 2)

(Compound Example 3)

(Compound Example 4)

(Compound Example 5)

(Compound Example 6)

(Compound Example 7)

(Compound Example 8)

(Compound Example 9)

(Compound Example 10)

(Compound Example 11)

(Compound Example 12)

(Compound Example 13)

(Compound Example 14)

(Compound Example 15)

(Compound Example 16)

(Compound Example 17)

(Compound Example 18)

[Polarizing components]

The polarizing component of the present invention contains a substrate and the aforementioned azo compound of the present invention. The azo compound of the present invention is preferably adsorbed on the aforementioned substrate. The azo compound that can be used as a pigment in the polarizing component of the present invention can usually be synthesized by a well-known diazo dye in accordance with the synthesis of azo dyes (for example, page 626 of Non-Patent Document 1) in this technical field. Manufactured by chemicalization and coupling. Dissolving the azo compound in the solution and impregnating the base material in the dyeing step can produce a polarizing component.

The polarizing device of the present invention preferably further contains an azo compound represented by the following general formula (3) or a salt thereof, which is a dichroic dye, in addition to the above-mentioned azo compound of the present invention.

Thereby, a polarizing component with higher polarizing performance can be realized. It is also preferable that the azo compound represented by the aforementioned general formula (3) or a salt thereof is adsorbed on the aforementioned substrate.

In the general formula (3), Ar ₁ represents a phenyl group with a substituent or a naphthyl group with a substituent, and Rr ₁ to Rr ₆ independently represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, and an alkyl group with 1 to 4 carbon atoms. An alkoxy group or an alkoxy group with 1 to 4 carbon atoms having a sulfonic acid group, Xr ₁ represents an amino group that may have a substituent (except for a phenyl group and a benzoyl group), a phenylamino group that may have a substituent, a substituent The benzoylamino group, the phenylazo group which may have a substituent, or the naphthotriazolyl group which may have a substituent, m and n each independently represent 0 or 1.

The azo compound represented by the aforementioned general formula (3) is preferably an azo compound represented by the following general formula (5).

(In the formula, Ab ₁ , Rb ₁ to Rb ₅ and Xb ₁ represent the same meanings as in the general formula (1))

In the aforementioned general formula (3) or (5), Ar ₁ represents a phenyl group with a substituent or a naphthyl group with a substituent, and Rr ₁ to Rr ₆ independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 4, or An alkoxy group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons having a sulfonic acid group, Xr ₁ represents an amino group which may have a substituent (excluding phenyl and benzoyl), a substituent which may have a substituent In the phenylamino group, the benzoylamino group which may have a substituent, the phenylazo group which may have a substituent, or the naphthotriazolyl group which may have a substituent, m and n each independently represent 0 or 1.

Rr ₁ to Rr ₆ in the aforementioned general formula (3) or (5) are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and are particularly preferably a hydrogen atom or a methyl group. For Rr ₅ and Rr ₆ in the aforementioned general formula (3) or (5), one is an alkoxy group with 1 to 4 carbons, and the other is an alkyl group with 1 to 4 carbons or an alkane with 1 to 4 carbons. Oxygen is preferred.

Xr ₁ in the aforementioned general formula (3) or (5) may preferably have one or more selected from the group consisting of methyl, methoxy, sulfonic acid, amino and alkylamino with 1 to 4 carbons. The phenylamino group with two substituents may have one substituent selected from the group consisting of hydroxyl group, amino group, and carboxyethylamino group. The benzoylamino group may have one substituent selected from the group consisting of hydroxyl group and alkyl group having 1 to 4 carbon atoms. , phenylazo group with 1 to 3 substituents in the group consisting of alkoxy group with 1 to 4 carbon numbers, amino group and carboxyethylamino group, or naphthotrizo group substituted with 1 or 2 sulfonic acid groups Azolyl; More preferably, it may have 1 or 2 substituents of phenylamino group selected from the group consisting of methyl, methoxy, sulfonic acid, amino and alkylamino with carbon number 1 to 4, may have A benzoylamino group with one substituent selected from the group consisting of hydroxyl, amino group, and carboxyethylamino group, or a naphthotriazolyl group substituted by one or two sulfonic acid groups; phenylamino group consisting of one or two substituents from the group consisting of methoxy group, sulfonic acid group and amino group, or may have one substituent selected from the group consisting of hydroxyl group, amino group and carboxyethylamino group of benzoylamino.

Ar ₁ in the aforementioned general formula (3) or (5), although it is a substituted phenyl group or a substituted naphthyl group, may have an alkyl group selected from a sulfonic acid group, a carboxyl group, and a carbon number of 1 to 4 and a phenyl group with one or two substituents in the group consisting of an alkoxy group with a carbon number of 1 to 4, or an alkoxy group with a carbon number of 1 to 4 selected from a sulfonic acid group, a hydroxyl group, and a sulfonic acid group The naphthyl group with 2 or 3 substituents is preferred.

In Ar in _the aforementioned general formula (3) or (5), the substituent on the phenyl group is a sulfonic acid group, a carboxyl group, an alkyl group with a carbon number of 1 to 4, an alkoxyl group with a carbon number of 1 to 4, or a hydroxyl group. , an alkoxy group having a sulfonic acid group having 1 to 4 carbon atoms, a naphthotriazolyl group substituted with a sulfonic acid group, a nitro group, an amino group, an acetylamino group, or an alkylamino group having a carbon number of 1 to 4 are preferred. In Ar ₁ in the aforementioned general formula (3) or (5), the substituent on the naphthyl group is preferably a sulfonic acid group, a hydroxyl group, or an alkoxy group with 1 to 4 carbon atoms having a sulfonic acid group. Ar ₁ in the aforementioned general formula (3) or (5) is preferably a phenyl or naphthyl group having one or more sulfonic acid groups or carboxyl groups, and is preferably a phenyl or naphthyl group having two or more sulfonic acid groups in order to improve durability. A phenyl group or a carboxyl group or a naphthyl group is more preferable. Ar ₁ in the above-mentioned general formula (3) or (5) is more preferably a phenyl group having a sulfonic acid group or a carboxyl group in order to further improve the polarizing characteristics and to manufacture a neutral color polarizing device.

Although m and n in the general formula (3) are as long as they are independently 0 or 1, but when desired to obtain good polarizing performance in the polarizer assembly of the present invention, at least one of m and n is preferably 1, more preferably Preferably both m and n are 1. In addition, the substituted amino group is not particularly limited, but may include, for example, an amino group substituted with an alkyl group or an acyl group having 1 to 4 carbon atoms. In addition, although the substituted amide group is not particularly limited, it may contain an amide group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.

The synthesis method of the azo compound represented by the aforementioned general formula (3) or its salt can be used, for example, in Japanese Patent Application Laid-Open No. 9-302250, Japanese Patent No. 4662853, International Publication No. 2012/108169, International Publication No. 2012/ No. 108173 etc. described methods, but not limited to these methods.

The azo compound represented by the aforementioned general formula (3) or its salt can be exemplified as C.I. Direct Red 81, C.I. Direct Red 117, C.I. Direct Red 127, azo compounds described in International Publication No. The azo compound described in Example 1 of Publication No. 2005/075572), the dye described in Japanese Patent No. 4662853, the dye described in International Publication No. 2013/008735, and the dye described in Japanese Patent Publication No. 2-61988 The azo compound described in Japanese Patent Application Laid-Open No. 2013-57909, the azo compound described in International Publication No. 2012/108169 (such as the formula (8) and (9) of International Publication No. 2012/108169 ), (10), (17), (21) represented azo compounds) etc., but not limited to these.

The azo compound represented by the above-mentioned general formula (3) or its salt can be contained in the polarizer in the form of free acid represented by the above-mentioned general formula (3), and the azo compound represented by the above-mentioned general formula (3) can also be The salt form is contained in the polarizer assembly. The aforementioned salts may be alkali metal salts such as lithium salts, sodium salts, and potassium salts, or organic salts such as ammonium salts or alkylamine salts. The above-mentioned salts are preferably lithium salts or sodium salts, and more preferably sodium salts.

Next, specific examples of the azo compound represented by the general formula (3) or a salt thereof that can be used in the polarizing device of the present invention will be given below. In addition, in the following compound examples, substituents such as a sulfonic acid group, a carboxyl group, and a hydroxyl group are shown in the form of free acids, but these substituents may also be in the form of salts. (Compound Example 19)

(Compound Example 20)

(Compound Example 21)

(Compound Example 22)

(Compound Example 23)

(Compound Example 24)

(Compound Example 25)

(Compound Example 26)

(Compound Example 27)

(Compound Example 28)

(Compound Example 29)

(Compound Example 30)

(Compound Example 31)

(Compound Example 32)

(Compound Example 33)

(Compound Example 34)

(Compound Example 35)

(Compound Example 36)

(Compound Example 37)

(Compound Example 38)

(Compound Example 39)

(Compound Example 40)

(Compound Example 41)

(Compound Example 42)

(Compound Example 43)

(Compound Example 44)

(Compound Example 45)

(Compound Example 46)

(Compound Example 47)

(Compound Example 48)

(Compound Example 49)

(Compound Example 50)

(Compound Example 51)

(Compound Example 52)

(Compound Example 53)

(Compound Example 54)

(Compound Example 55)

(Compound Example 56)

(Compound Example 57)

(Compound Example 58)

(Compound Example 59)

(Compound Example 60)

(Compound Example 61)

(Compound Example 62)

(Compound Example 63)

(Compound Example 64)

(Compound Example 65)

(Compound Example 66)

(Compound Example 67)

(Compound Example 68)

(Compound Example 69)

(Compound Example 70)

(Compound Example 71)

(Compound Example 72)

(Compound Example 73)

(Compound Example 74)

(Compound Example 75)

(Compound Example 76)

(Compound Example 77)

(Compound Example 78)

(Compound Example 79)

(Compound Example 80)

(Compound Example 81)

(Compound Example 82)

(Compound Example 83)

(Compound Example 84)

(Compound Example 85)

(Compound Example 86)

(Compound Example 87)

(Compound Example 88)

(Compound Example 89)

(Compound Example 90)

(Compound Example 91)

(Compound Example 92)

(Compound Example 93)

(Compound Example 94)

(Compound Example 95)

(Compound Example 96)

(Compound Example 97)

(Compound Example 98)

(Compound Example 99)

(Compound Example 100)

(Compound Example 101)

(Compound Example 102)

(Compound Example 103)

(Compound Example 104)

(Compound Example 105)

(Compound Example 106)

(Compound Example 107)

In the polarizing component of the present invention, relative to 100 parts by weight of the azo compound represented by the general formula (1) or its salt of the present invention, the content of the azo compound represented by the aforementioned general formula (3) or its salt is expressed in terms of 1 It is preferable to exist in the range of 200 weight part, and it is more preferable to exist in the range of 50 to 100 weight part.

The polarizing component of the present invention preferably further contains an azo compound represented by the following general formula (4) or a salt thereof in addition to the azo compound represented by the general formula (1) or a salt thereof of the present invention described above,

And it is more preferable to contain two kinds of the azo compound represented by the said general formula (3) or its salt and the said azo compound represented by the said general formula (4) or its salt further. Thereby, a polarizing component with a higher degree of polarization can be realized. It is also preferable that the azo compound represented by the aforementioned general formula (4) or a salt thereof is adsorbed on the aforementioned substrate.

In the aforementioned general formula (4), Ay ₁ represents a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkyl group with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons, and Ry ₁ to Ry ₄ independently represent a hydrogen atom, A sulfonic acid group, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons, p represents an integer of 1 to 3. Ay ₁ in the aforementioned general formula (4) is preferably a carboxyl group or a sulfonic acid group.

The synthesis method of the azo compound represented by the aforementioned general formula (4) or its salt, although for example the synthesis method described in Non-Patent Document 1 or the synthesis method described in International Publication No. 2007/138980 can be used, it is not limited to these methods.

The azo compound or its salt represented by the aforementioned general formula (4) can be used, for example: C.I. Direct Yellow 12, C.I. Direct Yellow 72, C.I. Direct Orange 39 (CAS No.: 1325-54-8), International Publication No. 2007/138980 No. (for example, the azo compound of Compound Example 111 described in Example 1 of International Publication No. 2007/138980), but not limited to these compounds.

The azo compound represented by the above-mentioned general formula (4) or its salt can be contained in the polarizer in the form of free acid represented by the above-mentioned general formula (4), and the azo compound represented by the above-mentioned general formula (4) can also be The salt form is contained in the polarizer assembly. The aforementioned salts may be alkali metal salts such as lithium salts, sodium salts, and potassium salts, or organic salts such as ammonium salts or alkylamine salts. The above-mentioned salts are preferably lithium salts or sodium salts, and more preferably sodium salts.

Next, specific examples of the azo compound represented by the general formula (4) or a salt thereof that can be used in the polarizing device of the present invention will be given below. In addition, in the following compound examples, although the sulfonic acid group and the carboxyl group are shown in the form of free acids, the sulfonic acid group and the carboxyl group may be in the form of salts.

(Compound Example 108)

(Compound Example 109)

(Compound Example 110)

(Compound Example 111)

In the polarizing component of the present invention, relative to 100 parts by weight of the azo compound represented by the general formula (1) or its salt of the present invention, the content of the azo compound represented by the aforementioned general formula (4) or its salt is expressed in terms of 1 It is preferable to exist in the range of 200 weight part, and it is more preferable to exist in the range of 50 to 100 weight part.

In the polarizing element of the present invention, other organic dyes other than azo compounds or salts thereof represented by one or more general formulas (1), (3) and (4) may be used in combination with color adjustment and the like (for example, non-patent literature 2, etc.) and the azo compound represented by the general formula (1) of the present invention or a salt thereof. Other organic dyes used in combination are not particularly limited, but preferably dye hydrophilic polymers and belong to a wavelength region different from the absorption wavelength region of the azo compound or its salt represented by the general formula (1) of the present invention. Dyes with absorbing properties and high dichroism. Other organic dyes include, for example, azo compounds described in Non-Patent Document 2 (for example, C.I. Direct Yellow 28), or C.I. Direct Red 2, C.I. Direct Red 31, C.I. Direct Red 79, C.I. Direct Red 247, C.I. Green 80, C.I. Direct Green 59, C.I. Direct Blue 202, C.I. Direct Purple 9, etc. These azo compounds can be used in the form of free acids or in the form of salts such as alkali metal salts (for example, sodium salts, potassium salts, lithium salts), ammonium salts, and amine salts. When other organic dyes are used in combination with other organic dyes, according to which one of the target polarizing component belongs to a more neutral color polarizing component, a characteristic color polarizing component, a color polarizing component for a liquid crystal projector, or other color polarizing components, each is prepared. The types of other organic dyes are different. The blending amount of other organic dyes (the total blending amount of these organic dyes in the case of two or more kinds) is not particularly limited, but in general, relative to the azo compound or its salt represented by the general formula (1) of the present invention The total amount of the azo compound represented by the general formula (3) or its salt and the azo compound represented by the general formula (4) or its salt is 100 parts by weight, preferably in the range of 0.1 to 10 parts by weight.

The aforementioned substrate is preferably a hydrophilic polymer. The aforementioned hydrophilic polymer is not particularly limited, but examples include polyvinyl alcohol or its derivatives, amylose-based resins, starch-based resins, cellulose-based resins, polyacrylate-based resins, etc. . The substrate containing the azo compound of the present invention is most preferably polyvinyl alcohol or its derivatives (hereinafter referred to as "polyvinyl alcohol-based resin") in terms of dyeability, crosslinkability, and the like. The substrate is made into a film, the azo compound and other formulations of the present invention are adsorbed on the film-shaped substrate, and orientation treatment such as stretching is applied, thereby producing the polarizing device of the present invention.

The method for producing the polyvinyl alcohol-based resin is not particularly limited, and known production methods can be employed. The production method of polyvinyl alcohol resin can be obtained by saponifying polyvinyl acetate resin (homopolymer or copolymer of vinyl acetate), for example. Examples of polyvinyl acetate-based resins include copolymers of vinyl acetate and other monomers that can be copolymerized with vinyl acetate, in addition to polyvinyl acetate that is a homopolymer of vinyl acetate. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The polyvinyl alcohol or its derivatives can be further modified, such as polyvinyl formal or polyvinyl acetal modified with aldehydes.

The degree of saponification of the polyvinyl alcohol-based resin is usually preferably 85% or higher, more preferably 95 mol% or higher, still more preferably 99 mol% or higher, and particularly preferably 99.5 mol% or higher. If the degree of saponification is less than the above lower limit, the polyvinyl alcohol-based resin is likely to be eluted, causing in-plane unevenness in optical properties, lowering of dyeability in the dyeing process, and occurrence of cutting in the stretching process, which may significantly reduce productivity. , so it is not good.

When it is desired to improve the optical properties of the polarizing device of the present invention, the degree of polymerization of the polyvinyl alcohol-based resin is preferably 1,000 to 10,000, more preferably 2,000 to 10,000, more preferably 3,500 to 10,000, and especially 5,000 to 10,000 preferred. When the degree of polymerization exceeds 10,000, the polyvinyl alcohol-based resin becomes hard, film-forming properties and stretchability decrease, and productivity decreases. Therefore, from an industrial viewpoint, the degree of polymerization is preferably 10,000 or less. The degree of polymerization of a polyvinyl alcohol-based resin means a viscosity average degree of polymerization, and can be obtained by a well-known method in the technical field.

Hereinafter, a specific method for manufacturing a polarizing element will be described by taking a case where the base material is a film formed of a polyvinyl alcohol-based resin as an example.

First, a raw film made of a polyvinyl alcohol-based resin is obtained by forming a polyvinyl alcohol-based resin into a film. The film-forming method of polyvinyl alcohol-based resin, although in addition to the method of melt-extruding the water-containing polyvinyl alcohol-based resin, can also be cast film-forming method, wet film-forming method (film formation by spouting into a poor solvent method), gel film-forming method (a method of extracting and removing the solvent after the aqueous solution of polyvinyl alcohol-based resin is temporarily cooled and gelled), casting film-forming method (making an aqueous solution of polyvinyl alcohol-based resin flow on the substrate , drying method) and methods obtained by combining these methods, etc., but are not limited to these methods.

When a solvent is used for film formation, the solvent is not particularly limited, and examples include: dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol , diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, water, etc. The solvent may be used alone or in combination of two or more. The amount of the solvent used for film formation is preferably 70 to 95% by weight relative to the entire film-forming stock solution (mixture containing polyvinyl alcohol-based resin and solvent used for film formation), but is not limited. However, if the amount of the solvent is less than 70% by weight, the viscosity of the film-forming stock solution becomes high, making it difficult to filter or defoam during preparation, and it is difficult to obtain a raw film without foreign matters or defects. In addition, when the amount of the solvent exceeds 95% by weight, the viscosity of the film-forming stock solution becomes too low, and it is difficult to control the target thickness, and the influence of surface fluctuations caused by the wind during drying becomes larger, and the drying time becomes longer and the production reduced sex.

Plasticizers may also be used when making virgin films. Examples of the aforementioned plasticizer include glycerin, diglycerin, ethylene glycol, propylene glycol, and low-molecular-weight polyethylene glycol, but are not limited to these compounds. The usage-amount of the said plasticizer is not specifically limited, Usually, it is suitable in the range of 5-15 weight part with respect to 100 weight part of polyvinyl alcohol resins.

The method of drying the raw film after film formation includes, for example, drying with hot air, contact drying with a hot roll, or drying with an infrared heater, but is not limited thereto. One of these drying methods may be used alone, or two or more of them may be used in combination. The drying temperature is not particularly limited, but is preferably in the range of 50 to 70°C.

It is preferable to heat-treat the raw film after drying to control its swelling degree within a predetermined range described later. The heat treatment method of the raw film after film formation includes, for example, a method of using hot air, a method of bringing the raw film into contact with a hot roll, etc., but it is not particularly limited as long as it can be treated by heat. One of these methods may be used alone, or two or more of them may be used in combination. The heat treatment temperature is not particularly limited, but is preferably in the range of 110 to 140°C. The heat treatment time is usually about 1 to 10 minutes, but it is not particularly limited.

The thickness of the virgin film thus obtained is preferably 20 to 100 μm, more preferably 20 to 80 μm, and still more preferably 20 to 60 μm. When the thickness is less than 20 μm, film breakage tends to occur. When the thickness exceeds 100 µm, the stress applied to the film during stretching becomes large, and the mechanical load in the stretching step becomes large, requiring a large-scale device capable of withstanding the load.

The following swelling process was implemented with respect to the virgin film which consists of polyvinyl-alcohol-type resin obtained as mentioned above.

The aforementioned swelling step is carried out by immersing the virgin film formed of polyvinyl alcohol-based resin in a solution at 20 to 50° C. for 30 seconds to 10 minutes. The aforementioned solution is preferably an aqueous solution. Since the swelling of the film also occurs during the dyeing treatment of the azo compound, the swelling step can also be omitted when it is desired to shorten the time for manufacturing the polarizing element.

The swelling degree F of the virgin film is preferably 180 to 260%, more preferably 200 to 240%, and still more preferably 210 to 230%. When the degree of swelling F is less than 200%, the elongation at the time of stretching becomes small, and the possibility of cracking at a low magnification becomes high. When it is less than 180%, the elongation at the time of stretching is significantly reduced, the possibility of cracking becomes high, and sufficient stretching becomes difficult. On the other hand, if the degree of swelling F exceeds 240%, it becomes excessively swollen, wrinkles or slack occur, and it gradually becomes a cause of cutting during stretching. If the swelling degree F exceeds 260%, it is unfavorable because it obviously causes wrinkles or sagging. When it is desired to control the degree of swelling F, for example, an appropriate degree of swelling F can be achieved by means of the temperature and time when heat-treating the raw film after film formation.

The degree of swelling F of the raw film can be measured by a method well known in the technical field, for example, it can be measured by the following method. First, the raw film was cut into 5 cm×5 cm, and immersed in 1 L of distilled water at 30° C. for 4 hours. The soaked membrane was taken out from distilled water, and the water droplets on the surface of the membrane were absorbed by the filter paper between two pieces of filter paper, and then the weight [β (g)] of the membrane once immersed in water was measured. Then, the film impregnated and absorbed water droplets was dried using a dryer at 105° C. for 20 hours, cooled in a desiccator for 30 minutes, and then the weight [γ (g)] of the dried film was measured. Then, the degree of swelling F of the raw film was calculated by the following formula (v).

Swelling degree F=100×β/γ(%)…(v)

After the swelling step, the staining step is performed. In the dyeing step, the azo compound of the present invention (the azo compound represented by the general formula (1) or its salt) may be combined with other azo compounds (the azo compound represented by the general formula (3) or its salt) as needed. , the azo compound represented by the general formula (4) or its salt, etc.) are adsorbed together on the polyvinyl alcohol-based resin film.

The dyeing step is not particularly limited as long as it is a method of adsorbing the azo compound to the polyvinyl alcohol-based resin film. For example, it can be performed by immersing the polyvinyl alcohol-based resin film in a solution containing the azo compound. The solution temperature in this dyeing step is preferably 5 to 60°C, more preferably 20 to 50°C, and particularly preferably 35 to 50°C. The time of immersion in the solution can be moderately adjusted, but it is preferably 30 seconds to 20 minutes, and more preferably 1 to 10 minutes. The dyeing method is preferably a method of immersing the polyvinyl alcohol-based resin film in the solution, and may be a method of applying the solution to the polyvinyl alcohol-based resin film.

A solution containing an azo compound belonging to a dichroic dye may contain sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, anhydrous sodium sulfate, sodium tripolyphosphate, etc. as a dyeing aid. The content of these dyeing auxiliaries can be adjusted to any concentration according to the dyeing time and temperature due to the dyeability of the azo compound, but it is preferably 0 to 5% by weight, and more preferably 0.1 to 2% by weight.

After the dyeing step, a washing step (hereinafter referred to as "washing step 1") may be performed before proceeding to the next step. Washing step 1 is a step of washing away the dye solvent adhering to the surface of the polyvinyl alcohol-based resin film in the dyeing step with a washing solution. By carrying out the washing step 1, it is possible to suppress the transfer of the dye to the liquid to be treated next. In the washing step 1, water is generally used as a washing liquid. As a cleaning method, a method of immersing in a cleaning solution is preferred, but a method of applying a cleaning solution to a polyvinyl alcohol-based resin film may also be used. The washing time is not particularly limited, but is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds. The temperature of the cleaning solution in the cleaning step 1 must be such that the hydrophilic polymer does not dissolve, and is usually 5 to 40°C.

After the dyeing step or the washing step 1, a step of adding a crosslinking agent and/or a water-resistant agent to the polyvinyl alcohol-based resin film may be performed. As the above-mentioned crosslinking agent, for example, boron compounds such as boric acid, borax or ammonium borate, polyaldehydes such as glyoxal or glutaraldehyde, polyisocyanate systems such as biuret type, isocyanurate type, or block type can be used. Compounds, titanium-based compounds such as titanyl sulfate, etc., although ethylene glycol glycidyl ether, polyamide epichlorohydrin, etc. can also be used, but boric acid is preferred. Examples of the aforementioned water resistance agent include succinic acid peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride, or magnesium chloride. Wait.

Using at least one kind of crosslinking agent and/or water resistance agent shown above, the step of making the polyvinyl alcohol-based resin film contain a crosslinking agent and/or water resistance agent is performed. The aforementioned crosslinking agent and/or water resistance agent are usually used in the state of a solution dissolved in a solvent. The aforementioned solvent is preferably water, but is not limited thereto. In the step of containing the aforementioned crosslinking agent and/or water resistance agent, the concentration of the crosslinker and/or water resistance agent in the solvent is preferably 0.1 to 6.0% by weight relative to the solvent when boric acid is used as an example. , and more preferably from 1.0 to 4.0% by weight. The temperature of the solvent in this step is preferably 5 to 70°C, more preferably 5 to 50°C. The method of making the polyvinyl alcohol-based resin film contain a crosslinking agent and/or a water-resistant agent is preferably a method of immersing the polyvinyl alcohol-based resin film in a solution of a cross-linking agent and/or a water-resistant agent. This is a method of applying or coating this solution on a polyvinyl alcohol-based resin film. The processing time of this step is preferably 30 seconds to 6 minutes, and more preferably 1 to 5 minutes. However, it is not necessary to include a crosslinking agent and/or a water-resistant agent in the polyvinyl alcohol-based resin film. Therefore, when the production time of the polarizer is to be shortened, or when the cross-linking treatment or water-resistant treatment is not required, this treatment can also be omitted. step.

The stretching step is performed after the dyeing step, after the washing step 1, or after the step containing a crosslinking agent and/or a water-resistant agent. The stretching step is a step of stretching the polyvinyl alcohol-based resin film uniaxially. The stretching method may be either a wet stretching method or a dry stretching method. Although the present invention can be achieved as long as the extension ratio is 3 times or more, it is preferably 5 times to 7 times.

In the dry stretching method, when the stretching heating medium is air medium, the temperature of the air medium during stretching is preferably from room temperature to 180°C. In addition, it is preferable to carry out the stretching treatment in ambient air with a humidity of 20 to 95%RH. The stretching method includes, for example, a roll-to-roll zone stretching method, a roll heating stretching method, a press stretching method, an infrared heating stretching method, etc., but the stretching method is not limited thereto. The elongation step may be performed by one-stage elongation, or may be performed by two or more multi-stage elongation.

In the wet stretching method, the polyvinyl alcohol-based resin film is stretched in water, a water-soluble organic solvent, or a mixed solution thereof. Furthermore, it is preferable to carry out the stretching treatment while immersing the polyvinyl alcohol-based resin film in a solution containing the aforementioned crosslinking agent and/or water resistance agent. As the crosslinking agent, for example, boron compounds such as boric acid, borax or ammonium borate, polyaldehydes such as glyoxal or glutaraldehyde, polyisocyanates such as biuret type, isocyanurate type, or block type can be used. Compounds, titanium-based compounds such as titanyl sulfate, and others such as ethylene glycol glycidyl ether, polyamide epichlorohydrin, and the like can also be used. Examples of the aforementioned water resistance agent include succinic acid peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride, or magnesium chloride. Wait.

Using at least one of the crosslinking agents and/or water resistance agents shown above, the step of adding the crosslinking agent and/or water resistance agent to the polyvinyl alcohol-based resin film is performed. The aforementioned crosslinking agent and/or water resistance agent are usually used in the state of a solution dissolved in a solvent. The aforementioned solvent is preferably water, but is not limited thereto. Contains the aforementioned crosslinking agent and/or water resistance agent

The stretching of the polyvinyl alcohol-based resin film is performed in a solution containing at least one of the above-mentioned crosslinking agents and/or water resistance agents. The aforementioned crosslinking agent is preferably boric acid. The concentration of the cross-linking agent and/or water resistance agent in the aforementioned extending step is preferably, for example, 0.5 to 15% by weight, and more preferably 2.0 to 8.0% by weight. The extension ratio is preferably 2 to 8 times, and more preferably 5 to 7 times. The extension temperature is preferably 40 to 60°C, and more preferably 45 to 58°C. The extension time is usually 30 seconds to 20 minutes, but more preferably 2 to 5 minutes. The wet stretching step may be performed by one-stage stretching, or may be performed by multi-stage stretching of two or more stages.

After the stretching step, since the cross-linking agent and/or water-resistant agent may be deposited on the surface of the membrane, or foreign substances may be adsorbed, a cleaning step (hereinafter referred to as "cleaning step 2") to clean the surface of the membrane may be performed. . The washing time is preferably from 1 second to 5 minutes. The washing method is preferably a method of immersing in a washing liquid, but a method of applying or coating a washing liquid to a polyvinyl alcohol-based resin film may also be used. The cleaning treatment may be performed in one stage or in multistage treatment of two or more stages. The temperature of the cleaning solution in the cleaning step is not particularly limited, but is usually 5 to 50°C, preferably 10 to 40°C.

Solvents used in the treatment steps so far include, for example: water; Dimethyl sulfoxide; N-methylpyrrolidone; Methanol, ethanol, propanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol Alcohols such as alcohol, triethylene glycol, tetraethylene glycol, and trimethylolpropane; solvents such as amines such as ethylenediamine or diethylenetriamine, but are not limited to these solvents. Moreover, the mixture of 1 or more types of these solvents can also be used. The most preferred solvent is water.

After the stretching step or the washing step 2, a drying step of the polyvinyl alcohol-based resin film is performed. The drying process can be carried out by natural drying, but in order to further improve the drying efficiency, the moisture on the surface can be removed by compressing through rollers, air knife (air knife), suction roller, etc. In addition, it can also be used with such Air drying is performed together with the moisture removal, or instead of such moisture removal, air drying is performed. The temperature of the drying treatment is preferably 20 to 100°C, more preferably 60 to 100°C. The drying time may be within a range of 30 seconds to 20 minutes, but is preferably 5 to 10 minutes.

In the present invention, when it is desired to further improve the polarizing performance, iodine can be contained in the polarizing component by using, for example, iodine-containing dyeing solution to adsorb iodine on the substrate within the range of maintaining the desired durability. middle. The aforementioned staining solution contains iodine and iodide. As the aforementioned iodide, for example, potassium iodide, ammonium iodide, cobalt iodide, zinc iodide, etc. can be used, but it is not limited to the iodide shown here. The iodine concentration is preferably 0.0001 to 0.5% by weight, more preferably 0.001 to 0.4% by weight. The iodide concentration is preferably 0.0001 to 8% by weight. As the treatment step at this time, for example, any one of the dyeing step, the washing step 1, the elongation step, and the washing step 2, or some of these steps can be used. The treatment temperature is preferably 5 to 60°C, more preferably 5 to 50°C, and particularly preferably 10 to 40°C. The treatment time, although moderately adjustable, is preferably adjusted to 30 seconds to 20 minutes, and more preferably 1 to 5 minutes.

As mentioned above, the polarizing device of the present invention has excellent polarizing performance because the azo compound represented by the aforementioned general formula (1) is used as the azo compound in the polarizing device containing the substrate and the azo compound.

[polarizer]

The polarizing plate of the present invention comprises the polarizing unit of the present invention and a transparent protective layer provided on at least one side of the polarizing unit.

The above-mentioned transparent protective layer may be provided as a coating layer made of a transparent polymer or a laminated layer of a transparent film. The transparent polymer or transparent film forming the transparent protective layer is preferably a transparent polymer or transparent film with high mechanical strength and good thermal stability. The transparent polymer or transparent film used in the transparent protective layer includes, for example, cellulose acetate resin such as triacetyl cellulose or diacetyl cellulose or its film, acrylic resin or its film, polyvinyl chloride resin or its film, nylon resin or its film, polyester resin or its film, polyarylate resin or its film, cyclic polyolefin resin or its film containing cyclic olefins such as norbornene as a monomer, polyethylene, Polypropylene, polyolefin having a ring system or a norbornene skeleton or a copolymer thereof, a polymer (or resin) whose main chain or side chain is imide and/or amide, or a film thereof, and the like. In addition, a resin having liquid crystallinity or a film thereof may be provided as the transparent protective layer. The thickness of the protective film is, for example, about 0.5 to 200 μm. One layer of resin or film can be placed on one side of the polarizing component, or more than two layers of the same or different kind of resin or film can be placed on one side of the polarizing component, or more than one layer of the same kind can be placed on both sides of the polarizing component Or different kinds of resins or films.

Adhesives can be used to bond the aforementioned transparent protective layer to the polarizing component. The aforementioned binder is not particularly limited, but polyvinyl alcohol binder is preferred. The aforementioned polyvinyl alcohol binders include, for example, GOHSENOL (registered trademark) NH-26 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), EXCEVAL (registered trademark) RS-2117 (manufactured by KURARAY Co., Ltd.), etc., but are not limited to on these. A crosslinking agent and/or a water resistance agent may be added to the aforementioned adhesive. In the polyvinyl alcohol binder, a maleic anhydride-isobutylene copolymer may be mixed, and in this case, a crosslinking agent may be further mixed if necessary. Examples of the maleic anhydride-isobutylene copolymer include: ISOBAM (registered trademark) #18 (manufactured by KURARAY Co., Ltd.), ISOBAM (registered trademark) #04 (manufactured by KURARAY Co., Ltd.), ammonia-modified ISOBAM (registered trademark) #104 (manufactured by KURARAY Co., Ltd.), ammonia-modified ISOBAM (registered trademark) #110 (manufactured by KURARAY Co., Ltd.), imidized ISOBAM (registered trademark) #304 (manufactured by KURARAY Co., Ltd.) , imidized ISOBAM (registered trademark) #310 (manufactured by Kuraray Co., Ltd.), etc. A water-soluble polyvalent epoxy compound can be used as the crosslinking agent mixed in the maleic anhydride-isobutylene copolymer as needed. As said water-soluble polyvalent epoxy compound, DENACOL EX-521 (made by Nagase ChemteX Co., Ltd.), TETRAD (registered trademark)-C (made by Mitsubishi Gas Chemical Co., Ltd.), etc. are mentioned, for example. In addition, known adhesives other than polyvinyl alcohol adhesives such as urethane-based adhesives, acrylic-based adhesives, and epoxy-based adhesives may be used as the adhesive. In addition, for the purpose of improving the adhesive force of the adhesive or improving the water resistance, additives such as zinc compounds, chlorides, and iodides may be contained in the adhesive at a concentration of about 0.1 to 10% by weight. Additives are not limited. After adhering the transparent protective layer with an adhesive on at least one side of the polarizing component, it is dried or heat-treated at a moderate temperature, thereby obtaining a polarizing plate.

The above-mentioned polarizing plate can also be attached to display devices such as liquid crystal display devices and organic electroluminescent display devices according to the situation, and can also be installed on the surface of a transparent protective layer that will become a non-exposed surface after bonding. Various functional layers that improve viewing angle and/or contrast, and layers or films that enhance brightness. When bonding a polarizing plate to these layers or films, or a display device, it is preferable to use an adhesive.

The polarizing plate may be a polarizing plate in which various well-known functional layers such as an antireflection layer, an antiglare layer, and a hard coat layer are provided on the other surface of the transparent protective layer, that is, the exposed surface. When producing such various functional layers, a coating method is preferable, but a method of laminating films having the functions via an adhesive or an adhesive may also be used. In addition, the above-mentioned functional layer can be used as a layer or film for controlling phase difference.

As mentioned above, the polarizing plate of the present invention is represented by the above-mentioned general formula (1) in a polarizing plate provided with a polarizing element containing a base material and an azo compound, and a transparent protective layer provided on at least one side of the aforementioned polarizing element. As the aforementioned azo compound, the azo compound has excellent polarizing properties.

The polarizing assembly and polarizing plate of the present invention can be used in display devices such as liquid crystal display devices. A display device using the polarizing assembly or polarizing plate of the present invention can become a display device with high contrast.

In addition, the polarizing component and the polarizing plate of the present invention are respectively provided with a protective layer or a functional layer and a support body as required, and are used in liquid crystal projectors, electronic calculators, clocks, notebook computers, word processors, liquid crystal televisions, polarized light Lenses, polarized glasses, car navigators, organic electroluminescent displays, and indoor and outdoor measuring instruments and indicators, etc.

In the application method of the polarizing plate of the present invention, the polarizing plate of the present invention can be attached to a support and used as a polarizing plate with a support. The aforementioned support preferably has a planar portion because a polarizing plate is attached thereto. In addition, the above-mentioned support is preferably a glass molded article because it is used for optical purposes. Examples of the aforementioned glass molded product include glass plates, lenses, prisms (for example, triangular prisms, cubic prisms, etc.) and the like. A polarizing plate is attached to the lens, which can be used as a condenser lens with a polarizing plate in an LCD camera. In addition, a polarizing plate is attached to the prism, which can be used as a polarizing beam splitter with a polarizing plate or a dichroic prism with a polarizing plate in an LCD camera. Alternatively, a polarizing plate may be attached to the liquid crystal cell. The material of the aforementioned glass molded article includes, for example, inorganic glass such as soda glass, borosilicate glass, crystal, and sapphire, or organic plastics such as acrylic resin and polycarbonate, but inorganic glass is preferred. . The thickness or size of the aforementioned glass plate may be a desired size. In addition, in a polarizing plate with a support having a support made of glass, when it is desired to further increase the light transmittance of the single plate, an antireflection layer (AR layer) is provided on one or both sides of the glass surface and the polarizing plate surface. preferred. On the surface of such a support, for example, the surface of the plane portion of the support, a transparent adhesive (adhesive) agent is coated, and then the polarizing plate of the present invention is attached to the coated surface. Alternatively, a transparent adhesive (adhesive) agent may be applied to the polarizing plate, and then the support may be attached to the applied surface. The adhesive (adhesive) agent used at this time is preferably an acrylate type, for example. In addition, when using this polarizing plate and retardation film in combination as an elliptical polarizing plate, the retardation plate side of the elliptical polarizing plate is usually attached to a support, but the polarizing plate side of the elliptically polarizing plate can also be pasted. in the support body.

[display screen]

The display device of the present invention includes the polarizing unit of the present invention or the polarizing plate of the present invention. In addition, the display device of the present invention can be made into a reflective type, a transmissive type, or a dual-purpose transmissive/reflective type equipped with, for example, a liquid crystal cell and the polarizing assembly of the present invention or the polarizing plate of the present invention disposed on one side or both sides of the liquid crystal cell. and other liquid crystal display devices. The above-mentioned liquid crystal cell is optional, and for example, a liquid crystal cell of an active matrix drive type represented by a thin film transistor type, a liquid crystal cell of a simple matrix drive type represented by a twisted nematic type or a super twisted nematic type, and the like can be used. LCD unit.

In addition, in the display device of the present invention, one or more suitable other optical members such as a prism array sheet (prismarray sheet) or lens array sheet, a light diffusion plate, or a backlight may also be arranged at appropriate positions. When installing the polarizing unit of the present invention, the polarizing plate of the present invention, or other optical members, these may be the same on both sides, or may be different on both sides.

The display device of the present invention can also be made into a display device having an adhesive layer on one or both sides of the polarizing assembly of the present invention or the polarizing plate of the present invention to adhere to other components such as liquid crystal cells. For the formation of the adhesive layer, suitable adhesive substances or adhesives can be used, and there is no special limitation. Examples of the constituent material of the adhesive layer include materials in which suitable polymers such as acrylic resins, silicone resins, polyesters, polyurethanes, polyamides, polyethers, fluororesins, and rubbers are used as matrix polymers.

The display device of the present invention can be used in liquid crystal displays such as twisted nematic (TN), super twisted nematic (STN), thin film transistor (TFT), vertical alignment (VA), and in-plane switching (IPS). The device as a whole, and other display devices.

[Example]

Hereinafter, although the present invention is described in more detail by means of examples, the present invention is not limited to the scope of these examples. In addition, the transmittance, degree of polarization, and contrast value of the polarizing elements and polarizing plates obtained in Examples and Comparative Examples were measured as follows.

[Measurement method of transmittance and degree of polarization of polarizer]

Let the transmittance at each wavelength of one polarizer be the individual transmittance Ts, and the transmittance at each wavelength when two polarizers are superimposed so that the absorption axis directions of these polarizers become the same as parallel The bit transmittance Tp and the transmittance at each wavelength when two polarizers are overlapped so that the absorption axes of these polarizers are perpendicular are defined as the vertical bit transmittance Tc. The respective transmittances Ts, Tp, and Tc were measured at each wavelength at intervals of 5 nm using a spectrophotometer ("U-4100" manufactured by Hitachi High-Technologies Co., Ltd.).

The degree of polarization ρ (%) of the polarizer is calculated from the parallel transmissivity Tp and the perpendicular transmissivity Tc by the following formula.

ρ={(Tp-Tc)/(Tp+Tc)} ^1/2 ×100

[Measurement method of transmittance, degree of polarization and contrast value of polarizing plate]

The transmittance obtained by correcting the transmittance at each wavelength of one polarizing plate is the single transmittance Ys, and when two polarizing plates are superimposed so that the absorption axis direction of these polarizing plates becomes the same The transmittance obtained by correcting the transmittance at each wavelength is the parallel transmittance Yp, and the transmittance at each wavelength when two polarizers are overlapped so that the absorption axes of these polarizers are perpendicular The transmittance obtained by sensitivity correction is set as the vertical bit transmittance Yc. Visual sensitivity correction is based on JIS Z8722:2009 with C light source 2° field of view and chromaticity function. The respective transmittances Ys, Yp, and Yc were measured at each wavelength at intervals of 5 nm using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech Co., Ltd.).

The degree of polarization Py (%) of the polarizing plate is calculated by the following equation (16) from the sensitivity-corrected parallel-position transmittance Yp and the sensitivity-corrected perpendicular-position transmittance Yc.

Py＝{(Yp-Yc)/(Yp+Yc)} ^1/2 ×100...(16)

The contrast value (CR) of the polarizing plate is calculated by the following equation (17) from the sensitivity-corrected parallel transmittance Yp and the visual sensitivity-corrected perpendicular transmittance Yc.

CR=Yp/Yc...(17)

[Example 1]

<Synthesis of Azo Compound of Compound Example 1>

Add 25.3 parts by weight of 4-aminobenzene-1,3-disulfonic acid to 500 parts by weight of water, cool and keep the temperature below 10°C, add 31.3 parts by weight of 35% by weight aqueous hydrochloric acid, and then add 6.9 parts by weight of sodium nitrite, It was diazotized by stirring at 5 to 10°C for 1 hour. In this regard, 10.7 parts by weight of 3-methylaniline dissolved in dilute hydrochloric acid aqueous solution was added as a primary coupling agent (coupling component), and while stirring at 10 to 30°C, sodium carbonate was added to make the pH 3, and the coupling was achieved by stirring again. After the reaction was completed, it was filtered to obtain 29.7 parts by weight of a monoazoamino compound represented by the following structural formula (18).

Add the monoazoamino compound of the obtained structural formula (18) to 400 parts by weight of water, dissolve it with sodium hydroxide, add 25.0 parts by weight of 35% by weight aqueous hydrochloric acid at 10 to 30°C, and then add 5.5 parts by weight of sodium nitrite , stirred at 20 to 30° C. for 1 hour, and diazotized. In this regard, 8.6 parts by weight of 3-methylaniline dissolved in dilute hydrochloric acid aqueous solution was added as a secondary coupling agent, while stirring at 20 to 30 ° C, sodium carbonate was added to make the pH 3, and then stirred to complete the coupling reaction, and filtered , 31.3 parts by weight of a disazoamino compound represented by the following structural formula (19) was obtained.

Add the bis-azo amino compound of the obtained structural formula (19) to 250 parts by weight of water, dissolve it with sodium hydroxide, add 20.0 parts by weight of 35% by weight aqueous hydrochloric acid at 20 to 30°C, and then add 4.4 parts by weight of sodium nitrite , stirred at 20 to 30° C. for 1 hour, and diazotized. To this end, 8.8 parts by weight of 2-methoxy-5-methylaniline dissolved in dilute hydrochloric acid aqueous solution was added as a coupling agent for three times, and while stirring at 20 to 30°C, sodium carbonate was added to make the pH 3.5, Stir again to complete the coupling reaction, and filter to obtain 32.6 parts by weight of a trisazoamino compound represented by the following structural formula.

Add the obtained trisazo amino compound of structural formula (20) to 200 parts by weight of water, dissolve it with sodium hydroxide, add 16.0 parts by weight of 35% aqueous hydrochloric acid at 20 to 30 ° C, and then add 3.5 parts by weight of sodium nitrite, This was diazotized by stirring at 20 to 30°C for 1 hour to obtain a diazotized trisazoamino compound. In addition, as a quaternary coupling agent, 16.1 parts by weight of 6-phenylamino-1-naphthol-3-sulfonic acid was added to 50 parts by weight of water, and dissolved with sodium carbonate as a weak base to obtain a 4th coupling agent The solution.

In this 4 times coupling agent solution, the diazonium compound of the trisazoamino compound obtained previously was kept at pH 8 to 10 and injected, stirred, and the coupling reaction was completed. Then, 30.5 parts by weight of monoethanolamine was added to an aqueous solution of 25 parts by weight of copper sulfate, and reacted at 95° C. for 10 hours to perform a copperization reaction until unreacted substances were not recognized by thin-layer chromatography. After the reaction, it was salted out with sodium chloride and filtered to obtain 46.4 parts by weight of the azo compound (copper tetrasazo compound) of compound example 1 as an example of the azo compound represented by the general formula (1).

＜Production of Polarizing Module＞

A polyvinyl alcohol film ("VF-PE#4000" manufactured by KURARAY Co., Ltd.; hereinafter referred to as "film") with a saponification degree of 99 mol% or more and a film thickness of 40 μm as a base material was immersed in warm water at 35°C. For 3 minutes, carry out swelling treatment. On the other hand, by mixing 1.0 parts by weight of an azo compound of Compound Example 1 as an azo compound represented by general formula (1) or a salt thereof, 1.0 parts by weight of anhydrous sodium sulfate as a dyeing auxiliary agent, and 2,000 parts by weight of water Mix and prepare a 40°C aqueous solution. The aforementioned swollen-treated membrane was immersed in this aqueous solution at 40° C. to adsorb the azo compound to the membrane.

After the azo compound-adsorbed film was washed with water, it was treated with boric acid for 1 minute with a 40° C. aqueous solution containing 2% by weight of boric acid. The boric acid treatment was performed for 5 minutes in an aqueous solution at 58° C. containing 3.0% by weight of boric acid while stretching the film obtained by the boric acid treatment to 5.0 times. While maintaining the film obtained by the boric acid treatment in a tense state, washing treatment was performed with normal temperature water for 20 seconds. The film obtained by the cleaning treatment was immediately dried at 60° C. for 5 minutes to obtain a film-shaped polarizer with a film thickness of 15 μm. A polarizer containing an azo compound represented by the general formula (1) or a salt thereof according to an example of the present invention was produced by the above method.

[Example 2]

<Synthesis of Azo Compound of Compound Example 17>

In addition to using 28.2 parts by weight of (7,8-disulfonic acid group-2H-naphtho[1,2-d]triazol-2-yl-)-1-naphthol-3-sulfonic acid as the 4th coupling agent Substituting 16.1 parts by weight of 6-phenylamino-1-naphthol-3-sulfonic acid, with the same operation as the synthesis of the azo compound of compound example 1 in Example 1, the compound represented by general formula (1) was obtained. Azo compound or its salt The azo compound (copper tetraazo compound) of Compound Example 17.

＜Production of Polarizing Module＞

A polarizing device was produced in the same manner as in Example 1 except that the azo compound of Compound Example 17 was used instead of the azo compound of Compound Example 1.

[Comparative example 1]

A polarizer was produced in the same manner as in Example 1, except that the azo compound described in Example 38 of JP-A-60-156759 was used instead of the azo compound in Compound Example 1.

[Comparative example 2]

A polarizer was manufactured in the same manner as in Example 1, except that the azo compound described in Example 1 of Japanese Patent Publication No. Sho 64-5623 was used instead of the azo compound in Compound Example 1.

In Table 1, the monomer transmittance Ts, the parallel transmittance Tp, the perpendicular transmittance Tc, and the polarization The measurement result of degree ρ.

[Table 1]

Ts(%) Tp(%) Tc(%) ρ(%) Example 1 44.05 38.33 0.482 98.75 Example 2 43.91 37.98 0.582 98.48 Comparative example 1 44.02 37.44 1.315 96.55 Comparative example 2 43.96 35.78 2.872 92.27

As can be seen from Table 1, using the polarizing components of the copperized azo compounds of Examples 1 and 2 of the present invention, compared with the known copperized azo compounds so far, the degree of polarization can be increased with the same degree of transmittance. Improve dramatically.

[Example 3]

First, a polyvinyl alcohol film ("VF-PE#4000" manufactured by KURARAY Co., Ltd.; hereinafter referred to as "film") with a saponification degree of 99% or more and a film thickness of 40 μm was immersed in a 35°C 3 minutes in warm water for swelling treatment. In addition, 2.0 parts by weight of the azo compound of Compound Example 1 as the azo compound represented by the general formula (1) or its salt, and the azo compound of Compound Example 20 as the azo compound represented by the general formula (3) or its salt Nitrogen compound (C.I. Direct Red 117) 0.5 parts by weight, the azo compound of Compound Example 111 (the azo compound described in Example 1 of International Publication No. 2007/138980) as an azo compound represented by general formula (4) or a salt thereof Nitrogen compound) 0.5 weight part, 1.0 weight part of sodium tripolyphosphate as dyeing auxiliaries, 1.0 weight part of anhydrous sodium sulfate, and 2,000 weight part of water, and prepared the aqueous solution of 40 degreeC. The aforementioned swollen-treated membrane was immersed in this aqueous solution at 40° C. to adsorb the azo compound to the membrane.

After the film on which the azo compound was adsorbed was washed with water, it was treated with boric acid for 1 minute with a 30° C. aqueous solution containing 2% by weight of boric acid. The boric acid treatment was performed for 5 minutes in a 58° C. aqueous solution containing 3.0% by weight of boric acid while extending the film obtained by the boric acid treatment to 5.0 times. While maintaining the film obtained by the boric acid treatment in a tense state, washing treatment was performed with normal temperature water for 20 seconds. The film obtained by the cleaning treatment was immediately dried at 60° C. for 5 minutes to obtain a film-shaped polarizer with a film thickness of 15 μm. A film containing an azo compound represented by the general formula (1) or a salt thereof, an azo compound represented by the general formula (3) or a salt thereof, and an azo compound represented by the general formula (4) or Polarizing components of its salt.

On both sides of the obtained polarizing element, an alkali-treated triacetyl cellulose film ("TD-80U" manufactured by Fuji Film Co., Ltd.; hereinafter referred to as "TAC") with a film thickness of 80 μm was bonded using a polyvinyl alcohol adhesive. Adhesion, thereby laminating with the composition of TAC/adhesive layer/polarizer component/adhesive layer/TAC. Thereby, a polarizing plate was obtained. The obtained polarizing plate was used as a measurement sample.

[Example 4]

In addition to using 3.0 parts by weight of the azo compound of Compound Example 17 used in Example 2 as the azo compound represented by the general formula (1) or its salt instead of 2.0 parts by weight of the azo compound of Compound Example 1, the same method as in Example 3 The same operation is used to produce an azo compound or a salt thereof represented by the general formula (1), an azo compound or a salt thereof represented by the general formula (3), and an azo compound or a salt thereof represented by the general formula (4) in the film Polarizing components, and at the same time make a polarizing plate, and use the made polarizing plate as a measurement sample.

[Example 5]

In addition to the azo compound represented by the general formula (3) or its salt, 1.0 parts by weight of the sodium salt of the azo compound of Compound Example 41 (the azo compound described in Example 1 of International Publication No. 2005/075572) was used instead Except for 0.5 parts by weight of the azo compound of compound example 20, the same operation as in Example 3 was performed to prepare a film containing an azo compound represented by the general formula (1) or a salt thereof, and an azo compound represented by the general formula (3). or its salt and the azo compound represented by the general formula (4) or its salt, a polarizing plate is produced simultaneously, and the produced polarizing plate is used as a measurement sample.

[Example 6]

In addition to the azo compound represented by the general formula (3) or a salt thereof, the azo compound of Compound Example 54 (the azo compound represented by the formula (21) described in Example 3 of International Publication No. 2012/108169) 1.6 Except for 0.5 parts by weight of the azo compound of Compound Example 20, the same operation as in Example 3 was used to prepare a film containing an azo compound represented by the general formula (1) or a salt thereof, represented by the general formula (3) in the film. Polarizers comprising an azo compound or its salt and an azo compound represented by the general formula (4) or its salt are produced simultaneously, and a polarizing plate is produced, and the produced polarizing plate is used as a measurement sample.

[Example 7]

In addition to the azo compound represented by the general formula (4) or its salt, 0.58 parts by weight of C.I. Direct Orange 39 (CAS number: 1325-54-8) having the structure of the aforementioned general formula (4) was used to replace the azo compound of Example 111. Except 0.5 parts by weight of the nitrogen compound, with the same operation as in Example 3, a film containing the azo compound represented by the general formula (1) or its salt, the azo compound represented by the general formula (3) or its salt, and the general formula (3) was produced. A polarizer of an azo compound represented by formula (4) or a salt thereof is produced simultaneously with a polarizing plate, and the produced polarizing plate is used as a measurement sample.

[Example 8]

In addition to the azo compound represented by the general formula (3) or its salt, 0.12 parts by weight of the azo compound of Compound Example 20 and the azo compound of Compound Example 99 (described in Example 1 of International Publication No. 2012/108169) are used. The azo compound represented by the formula (17)) 1.2 parts by weight is substituted for 0.5 parts by weight of the azo compound of Compound Example 20, and as the azo compound represented by the general formula (4) or a salt thereof, the compound having the aforementioned general formula (4) is used. C.I. Direct orange 39 (CAS number: 1325-54-8) 0.39 parts by weight of the structure of the azo compound 0.5 parts by weight of substitution compound example 111, with the same operation as in Example 3, the film containing the general formula (1 ) represented by the azo compound or its salt, the azo compound represented by the general formula (3) or its salt, and the polarizing component of the azo compound represented by the general formula (4) or its salt; A polarizing plate was used as a measurement sample.

[Example 9]

In addition to using C.I. Direct Yellow 28 (0.80 parts by weight) represented by the following structural formula as other organic dyes to replace 0.5 parts by weight of the azo compound of Compound Example 111 as the azo compound represented by the general formula (4) or its salt, with The same operation as in Example 3 was used to make a film containing an azo compound represented by the general formula (1) or a salt thereof, an azo compound represented by the general formula (3) or a salt thereof, and a general film having a polarizing function at almost the same wavelength. A polarizer of an azo compound represented by formula (4) or a salt thereof is produced simultaneously with a polarizing plate, and the produced polarizing plate is used as a measurement sample.

[Comparative example 3]

Except that the composition of the azo compound in Example 3 is changed to the composition of the azo compound described in Example 2 of Japanese Patent Application Laid-Open No. 11-218611, the same operation as in Example 3 was used to produce a polarizer, and at the same time A polarizing plate was produced, and the produced polarizing plate was used as a measurement sample.

[Comparative example 4]

Except that the composition of the azo compound in Example 3 was changed to the composition of the azo compound described in Example 3 of Japanese Patent No. 4162334, a polarizer was produced in the same manner as in Example 3, and a polarizer was produced at the same time. plate, and the prepared polarizing plate was used as a measurement sample.

[Comparative Example 5]

Except that the composition of the azo compound in Example 3 was changed to the composition of the azo compound described in Example 1 of Japanese Patent No. 4360100, a polarizer was produced in the same manner as in Example 3, and a polarizer was produced at the same time. plate, and the prepared polarizing plate was used as a measurement sample.

[Comparative Example 6]

Except not using the azo compound of Compound Example 1 belonging to the azo compound represented by the general formula (1), the same operation as in Example 3 was used to manufacture a polarizing unit and a polarizing plate, and the prepared polarizing plate was used as a measurement sample.

[Comparative Example 7]

In addition to using 1.8 parts by weight of an azo compound represented by the formula (17) of International Publication No. 2012/108169, which belongs to the same tetraazo compound as the azo compound of Compound Example 1, instead of the azo compound represented by the general formula (1), Except for the azo compound of Compound Example 1, a polarizing element and a polarizing plate were produced in the same manner as in Example 3, and the produced polarizing plate was used as a measurement sample.

In Table 2, the light sensitivity-corrected single transmittance Ys, the light-sensitivity-corrected parallel-position transmittance Yp, Vertical transmittance Tc, polarization degree Py and contrast value CR corrected by visual sensitivity.

[Table 2]

Ys(%) Yp(%) Yc(%) Py(%) CR Example 3 40.23 32.33 0.0371 99.89 871 Example 4 40.36 32.54 0.0423 99.87 769 Example 5 40.71 33.11 0.0313 99.91 1058 Example 6 40.44 32.68 0.0236 99.93 1385 Example 7 40.41 32.54 0.1201 99.63 271 Example 8 40.43 32.67 0.0256 99.92 1276 Example 9 40.45 32.56 0.1621 99.50 201 Comparative example 3 40.38 31.94 0.6756 97.91 47 Comparative example 4 40.69 32.60 0.5123 98.44 64 Comparative Example 5 40.61 32.09 0.8914 97.26 36 Comparative Example 6 40.53 22.61 10.242 61.36 2 Comparative Example 7 40.45 31.91 0.818 97.47 39

It can be seen from Table 2 that when the polarizing plates of Examples 3 to 9 of the present invention are compared with the polarizing plates of Comparative Examples 3 to 7, the polarizing performance and contrast are improved. In addition, even when the polarizing plates of Examples 3 to 9 were exposed to an environment of 85° C. and a relative humidity of 85% for 500 hours, no change in the transmittance or degree of polarization occurred.

From the above, it is obvious from the results of Examples 1 to 9 and Comparative Examples 1 to 7 that the optical characteristics of the polarizing plate and polarizing assembly of the present invention are improved compared with the conventional polarizing plate and polarizing assembly. In addition, it is evident from the results of Examples 3 to 9 above that the polarizing plate and polarizing unit of the present invention are highly durable polarizing units and polarizing plates. In addition, products such as display devices or polarized lenses using the polarizing component or polarizing plate of the present invention have good polarization characteristics and durability, so high reliability can be obtained.

Claims (13)

1. An azo compound, which is an azo compound represented by the following general formula (1) or a salt thereof: In the formula, Ab ₁ represents a phenyl group with a substituent or a naphthyl group with a substituent, and Rb ₁ to Rb ₅ independently represent a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, A sulfonic acid group, or an alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, Xb ₁ represents an amino group that may have a substituent, a phenylamino group that may have a substituent, a benzoylamino group that may have a substituent, or an amino group that may have a substituent. A phenylazo group which has a substituent, or a naphthotriazolyl group which may have a substituent. 2. The azo compound according to claim 1, which is an azo compound or a salt thereof represented by the following general formula (2): In the formula, Ab ₁ represents a phenyl group having one or two substituents selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkyl group with 1 to 4 carbons, and an alkoxy group with 1 to 4 carbons, or Naphthyl having 2 or 3 substituents selected from the group consisting of a sulfonic acid group, a hydroxyl group, and an alkoxy group having sulfonic acid groups with 1 to 4 carbon atoms; Rb ₁ to Rb ₅ independently represent a hydrogen atom, An alkyl group with 1 to 4 carbons, an alkoxy group _with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons with a sulfonic acid group; The phenylamino group with one or two substituents in the group consisting of radical, amino group and alkylamino group with 1 to 4 carbon atoms may have one substituent selected from the group consisting of hydroxyl group, amino group and carboxyethylamino group. benzoylamino group, which may have 1 to 3 substituents selected from the group consisting of hydroxyl, alkyl group with 1 to 4 carbons, alkoxy group with 1 to 4 carbons, amino group and carboxyethylamino group Phenylazo, or naphthotriazolyl substituted with 1 or 2 sulfonic acid groups. 3. the azo compound according to claim 1 or 2, wherein, _Xb in the general formula (1) or (2) can have a methyl group, a methoxyl group, a sulfonic acid group, an amino group and A phenylamino group having 1 or 2 substituents in the group consisting of an alkylamino group having 1 to 4 carbon atoms. 4. A polarizing component, comprising a substrate and the azo compound according to any one of claims 1 to 3. 5. The polarizing assembly according to claim 4, further comprising an azo compound or a salt thereof represented by the following general formula (3): In the formula, Ar ₁ represents a phenyl group with a substituent or a naphthyl group with a substituent, and Rr ₁ to Rr ₆ independently represent a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, or An alkoxy group having 1 to 4 carbon atoms having a sulfonic acid group, Xr ₁ represents an amino group that may have a substituent, a phenylamino group that may have a substituent, a benzoylamino group that may have a substituent, or a phenyl group that may have a substituent An azo group or a naphthotriazolyl group which may have a substituent, and m and n independently represent 0 or 1. 6. The polarizing assembly according to claim 4 or 5, further comprising an azo compound or a salt thereof represented by the following general formula (4): In the formula, Ay ₁ represents a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkyl group with a carbon number of 1 to 4, or an alkoxy group with a carbon number of 1 to 4, and Ry ₁ to Ry ₄ independently represent a hydrogen atom, a sulfonic acid group, and a carbon number An alkyl group of 1 to 4 or an alkoxy group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3. 7. The polarizing assembly according to claim 5, wherein, The azo compound or its salt represented by the general formula (3) is an azo compound or its salt represented by the following general formula (5): In the formula, _Ar represents a phenyl group having one or two substituents selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkyl group with 1 to 4 carbons, and an alkoxy group with 1 to 4 carbons, or Naphthyl having 2 or 3 substituents selected from the group consisting of a sulfonic acid group, a hydroxyl group, and an alkoxy group with sulfonic acid groups having 1 to 4 carbon atoms; Rr ₁ to Rr ₆ independently represent a hydrogen atom, An alkyl group with 1 to 4 carbons, an alkoxy group _with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons with a sulfonic acid group; The phenylamino group with one or two substituents in the group consisting of radical, amino group and alkylamino group with 1 to 4 carbon atoms may have one substituent selected from the group consisting of hydroxyl group, amino group and carboxyethylamino group. benzoylamino group, which may have 1 to 3 substituents selected from the group consisting of hydroxyl, alkyl group with 1 to 4 carbons, alkoxy group with 1 to 4 carbons, amino group and carboxyethylamino group Phenyl azo, or naphthotriazolyl substituted by 1 or 2 sulfonic acid groups; m and n independently represent 0 or 1. 8. The polarizer assembly according to claim 5 or 7, wherein, among Rr ₅ and Rr ₆ in the general formula (3) or (5), one is an alkoxy group with 1 to 4 carbons, and the other is An alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons. 9. The polarizer assembly according to claim 5 or 7, wherein _Xr in the general formula (3) or (5) can have A phenylamino group having one or two substituents from the group consisting of alkylamino groups with numbers 1 to 4, or a benzyl group that may have one substituent selected from the group consisting of hydroxyl, amino and carboxyethylamino groups Acylamino. 10. The polarizing assembly according to claim 6, wherein Ay ₁ in the general formula (4) is a carboxyl group or a sulfonic acid group. 11. The polarizing assembly according to any one of claims 4 to 10, wherein the base material is a film formed of polyvinyl alcohol or a derivative thereof. 12. A polarizing plate, comprising the polarizing unit according to any one of claims 4 to 11, and a transparent protective layer provided on at least one side of the polarizing unit. 13. A display device comprising the polarizing assembly according to any one of claims 4 to 11, or the polarizing plate according to claim 12.