KR20190134615A - Azo compound or its salt, and dye type polarizing film, dye type polarizing plate, and liquid crystal display device containing this - Google Patents

Abstract

(식 중, A¹ 및 A² 는 각각 독립적으로, 하이드록시기, 술포기를 갖는 C1 ∼ 4 알콕시기 및 술포기로 이루어지는 군에서 선택되는 치환기를 가져도 되는 나프틸기, 또는 치환기를 가져도 되는 페닐기이고, R₁ ∼ R₆ 은 각각 독립적으로 수소 원자, C1 ∼ 4 알킬기, C1 ∼ 4 알콕시기, 술포기를 갖는 C1 ∼ 4 알콕시기, 카르복시기, 하이드록시기, 할로겐기, 또는 C1 ∼ 4 알킬 치환 아실아미노기이다.)
로 나타내는 아조 화합물 또는 그 염을 제공한다.An object of this invention is to provide the azo compound useful as a dichroic dye used for a polarizing plate.
This invention is following formula (1):

(In formula, A <^1> and A <^2> may respectively independently have a naphthyl group which may have a substituent chosen from the group which consists of a hydroxyl group, the C1-4 alkoxy group which has a sulfo group, and a sulfo group, or a substituent. R ₁ to R ₆ are each independently a hydrogen atom, a C 1-4 alkyl group, a C 1-4 alkoxy group, a C 1-4 alkoxy group having a sulfo group, a carboxyl group, a hydroxyl group, a halogen group, or C 1-4 alkyl Substituted acylamino group.)
It provides an azo compound or a salt thereof.

Description

Azo compound or its salt, and dye type polarizing film, dye type polarizing plate, and liquid crystal display device containing this

The present invention relates to a novel azo compound or a salt thereof, and a dye polarizing film, a dye polarizing plate, and a liquid crystal display device containing the same.

A polarizing plate having a light transmission / shielding function is a basic component of a display device such as a liquid crystal display (LCD) together with a liquid crystal having a light switching function. The field of application of the LCD also includes notebook personal computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring equipment, and the like from small devices such as electronic desk calculators and clocks at an early stage. In addition, the present invention can be applied to a lens having a polarizing function, and has been applied to sunglasses having improved visibility and recently, polarizing glasses or the like corresponding to 3D televisions. Since the use of the above-mentioned polarizing plate is widening widely, since a polarizing plate is used on the wide conditions of low temperature-high temperature, low humidity-high humidity, low light quantity-high light quantity, the polarizing plate which has high polarization performance and high durability is used. It is required.

At present, a polarizing plate is used for polarizing film base materials, such as a polyene alcohol or its derivative, or a polyene film in which polyene is produced and orientated by dehydration of a polyvinyl chloride film or dehydration of a polyvinyl alcohol film. It is prepared by dyeing or containing iodine or dichroic dye. These are substances which greatly influence the polarization characteristics and durability in the polarizing plate. The iodine polarizing film using iodine has excellent polarization performance, but is weak against water and heat, and has a problem in durability when used for a long time in a high temperature and high humidity state. In order to improve durability, a method of treating with formalin or an aqueous solution containing boric acid, or using a polymer film having a low moisture permeability as a protective film has been considered, but the effect thereof cannot be said to be sufficient. On the other hand, the dye-based polarizing film using a dye is excellent in moisture resistance and heat resistance as compared to the iodine-based polarizing film, but generally the polarizing performance is not sufficient.

Until recently, in order to raise the sharpness of the image of a liquid crystal display, image display was carried out with high luminance. Since the demand for a longer driving time of the battery has been raised in hybrid cars and mobile terminals equipped with such a display, a polarizing plate that can maintain the brightness and clarity of an image even if the liquid crystal display manufacturer drops the luminance to lower power consumption. This has been required.

However, in a polarizing film obtained by adsorbing and aligning some kinds of dyes to a polymer film, if there is light leakage (color leakage) of a specific wavelength in the wavelength region of the visible light region, when the polarizing film is attached to the liquid crystal panel, In the (iii) state, the color of the liquid crystal display may change. Therefore, when the polarizing film is attached to the liquid crystal display device, in order to prevent discoloration of the liquid crystal display due to color leakage of a specific wavelength in the dark state, a neutral color polarizing film in which several kinds of dyes are dyed or contained in the polymer film is used. Therefore, the transmittance (orthogonal transmittance) of the orthogonal position in the wavelength region of the visible light region must be equally low. Moreover, in a vehicle liquid crystal display, since it becomes a high temperature, high humidity environment in a summer car, the polarizing plate which does not change polarization degree even if it is a severe environment is calculated | required. Previously, an iodine polarizing plate having good polarization performance and exhibiting neutral gray has been used. However, the iodine polarizing plate has a problem that the light resistance, heat resistance, and moisture heat resistance are not sufficient as described above. In order to solve this problem, the dye-based neutral gray polarizing plate which dyed or contains several types of dichroic dyes has been used. The dye-based neutral gray polarizing plate is generally used in combination of red, blue, and yellow dyes, which are three primary colors of light. However, as described above, the polarization performance of the dye-based neutral gray polarizing plate is not sufficient. Therefore, development of a dichroic dye with good polarization performance for each of three primary colors is required.

A characteristic of the dye system is that in order to control the components of the three primary colors of light as described above, each independent dye corresponding thereto is dyed or contained. Although light sources used in recent liquid crystal display panels include cold cathode tube systems, LED systems, and the like, the light source wavelengths emitted therefrom vary depending on the method, and in many cases, the same method may be different for each panel manufacturer. Therefore, in developing a dichroic dye with good polarization performance, it is particularly important to design a dichroic dye having an absorption wavelength that matches the wavelength of a light source.

As a dye used for manufacture of the said dye type polarizing film, the water-soluble azo compound described in patent document 1-patent document 6 etc. is mentioned, for example.

Japanese Laid-Open Patent Publication No. 03-12606 Japanese Unexamined Patent Publication No. 2001-33627 Japanese Unexamined Patent Publication No. 2009-132794 Japanese Unexamined Patent Publication No. 2001-240762 Japanese Unexamined Patent Publication No. 2001-108828 Japanese Laid-Open Patent Publication No. 60-156759

 Dye Chemistry P139-149; Hosoda Yutaka Published by Tsukuba, 1957

One object of the present invention is to provide a novel polarizing plate. Another object of the present invention is to provide a polarizing plate having excellent polarization performance. Another object of the present invention is to provide a polarizing plate having durability (moisture resistance, heat resistance, or light resistance). In addition, another object of the present invention is a neutral gray polarizing plate formed by adsorbing and aligning two or more kinds of dichroic dyes on a polymer film, and having no orthogonal color leakage in the wavelength region of the visible region, and excellent polarization. It is providing the polarizing plate which has performance.

A further object is to provide a high performance polarizing plate which is a dye-based neutral gray polarizing plate for on-vehicle liquid crystal display and has good brightness, polarization performance, and durability (moisture resistance, heat resistance, or light resistance).

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve this objective, the present inventors found out that the polarizing film and polarizing plate containing a specific azo compound or its salt have the outstanding polarizing performance, and completed this invention.

That is, this invention relates to the following (1)-(22).

(1) The following formula (1):

[Formula 1]

(In formula, A <^1> and A <^2> respectively independently have a naphthyl group which may have a substituent selected from the group which consists of a hydroxyl group, the C1-4 alkoxy group which has a sulfo group, and a sulfo group, or a substituent. Is a phenyl group,

R ₁ to R ₆ each independently represent a hydrogen atom, a C 1-4 alkyl group, a C 1-4 alkoxy group, a C 1-4 alkoxy group having a sulfo group, a carboxyl group, a hydroxyl group, a halogen group, or a C 1-4 alkyl substituted acylamino group to be)

Azo compound or its salt represented by these.

(2) one or both of A ¹ and A ² (in each case independently), a C 1-4 alkoxy group, a C 1-4 alkyl group, a C 1-4 alkoxy group, a halogen group having a sulfo group, a carboxy group, a sulfo group, C1-4 alkyl substituted amino groups such as nitro group, amino group, N, N-dimethylamino group, N, N-diethylamino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group and sec-butylamino group, and The azo compound as described in (1) or its salt which is a phenyl group which has one or more substituents chosen from the group which consists of C1-4 alkyl substituted acylamino groups, such as an acetylamino group, a propionamide group, and a butylamide group.

(3) One or both of A ¹ and A ² (in each case, each independently) has at least one substituent selected from a C1-4 alkoxy group having a sulfo group, a carboxy group, and a sulfo group, and a hydrogen atom, Addition of C1-4 alkoxy group, C1-4 alkyl group, C1-4 alkoxy group, halogen group, nitro group, amino group, C1-4 alkyl substituted amino group, or C1-4 alkyl substituted acylamino group having aeration, carboxyl group and sulfo group The azo compound as described in (1) or (2) which is a phenyl group which has, or its salt.

(4) Either one or both of A ¹ and A ² (when both are independently), the following formula (2):

[Formula 2]

(In formula, one of R <_7> and R <_8> is a C1-4 alkoxy group which has a sulfo group, a carboxyl group, or a sulfo group, and the other is a C1-4 alkoxy group, C1 which has a hydrogen atom, a sulfo group, a carboxy group, and a sulfo group. 4-4 alkyl group, C1-4 alkoxy group, halogen group, nitro group, amino group, C1-4 alkyl substituted amino group, or C1-4 alkyl substituted acylamino group)

The azo compound in any one of (1)-(3) which is a phenyl group shown by this, or its salt.

(5) The azo compound or salt thereof according to (4), wherein one of R ₇ and R ₈ is a sulfo group or a carboxyl group, and the other is a hydrogen atom, a sulfo group, a carboxyl group, a methyl group, or a methoxy group.

(6) The azo compound or salt thereof in any one of (1)-(5) whose at least one of A <^1> and A <^2> is the said naphthyl group.

(7) The azo compound in any one of (1)-(6) whose its both A <^1> and A <^2> is the said phenyl group, or its salt.

(8) Either one or both of A ¹ and A ² (when both are independently), the following formula (3):

[Formula 3]

(In formula, R <_9> is a C1-4 alkoxy group or sulfo group which has a hydrogen atom, a hydroxyl group, a sulfo group, and n is an integer of 1-3.)

The azo compound in any one of (1)-(6) which is a naphthyl group shown by these, or its salt.

(9) The azo compound as described in (8) or its salt whose R <_9> is a hydrogen atom and n is 2.

(10) The following formula (4):

[Formula 4]

(Wherein R ₁ to R ₆ are as defined in formula (1))

The azo compound as described in any one of (1)-(9) represented by this, or its salt.

(11) The following formula (5):

[Formula 5]

(In formula, at least 1 of R <_10> -R <_13> is a sulfo group, Other than that, it is a C1-4 alkoxy group, methyl group, or methoxy group which has a hydrogen atom, a sulfo group, a carboxyl group, a sulfo group, and R <_1> -R <_6> is As defined in equation (1))

The azo compound as described in any one of (1)-(5), or its salt.

(12) R <_1> -R <_6> is respectively independently any of (1)-(11) which is a C1-4 alkoxy group which has a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a halogen group, or a sulfo group. The azo compound or salt thereof described in the above.

(13) R <_1> -R <_6> is respectively independently C1-4 alkoxy group which has a sulfo group, a hydrogen atom, a methyl group, an ethyl group, a halogen group, or a methoxy group, as described in any one of (1)-(12) Azo compounds or salts thereof.

(14) The azo compound according to any one of (1) to (13) or a salt thereof, wherein at least one of R ₁ to R ₆ is a C 1-4 alkoxy group having a sulfo group.

(15) The azo compound or salt thereof according to (14), wherein the C1-4 alkoxy group having the sulfo group is a 3-sulfopropoxy group.

(16) The dye type polarizing film containing the polarizing film base material containing the azo compound in any one of (1)-(15) or its salt.

(17) The dye type polarizing film containing the azo compound in any one of (1)-(15) or its salt, and the polarizing film base material containing one or more types of organic dyes other than these.

The dye polarizing film as described in (16) or (17) whose said polarizing film base material is a film which consists of a polyvinyl alcohol resin or its derivative (s).

(19) The dye-based polarizing plate in which a transparent protective layer is bonded to one or both surfaces of the dye-based polarizing film according to any one of (16) to (18).

(20) The polarizing plate for liquid crystal display provided with the dye type polarizing film in any one of (16)-(18), or the dye type polarizing plate as described in (19).

(21) The neutral gray polarizing plate provided with the dye type polarizing film in any one of (16)-(18), or the dye type polarizing plate as described in (19).

(22) A liquid crystal display device comprising the dye-based polarizing plate according to (19), the polarizing plate for liquid crystal display according to (20), or the neutral gray polarizing plate according to (21).

The azo compound or its salt of this invention is useful as dye for polarizing films. And the polarizing film of this invention containing the said azo compound or its salt has high polarization performance comparable to the polarizing film using iodine. In one aspect, the polarizing film of this invention is excellent also in durability (moisture resistance, heat resistance, or light resistance). Therefore, it is suitable for the various liquid crystal display bodies and liquid crystal projectors, and the vehicle-use use which requires high polarization performance and durability, and the display use of the industrial instruments used in various environments.

<Azo compound>

The azo compound of this invention is represented by following formula (1).

[Formula 6]

A ¹ and A ² are each independently a naphthyl group which may have a substituent or a phenyl group having a substituent. In one aspect, both A ¹ and A ² are phenyl groups. In another embodiment, at least one of A ¹ and A ² is a naphthyl group which may have a substituent. When both of A ¹ and A ² are naphthyl groups which may have a substituent, the substituents of the naphthyl group may be the same or different. When both A ¹ and A ² are phenyl groups which may have a substituent, the substituents of the phenyl group may be the same or different. Here, in the specification of the present application and the claims, the "lower alkyl" in "lower alkyl" and "lower alkoxy" means having 1 to 4 carbon atoms. Moreover, it also shows as "C1-4."

The phenyl group having a substituent is preferably a lower alkoxy group having a sulfo group, a carboxy group, a sulfo group, a lower alkyl group, a lower alkoxy group, a halogen group, a nitro group, an amino group, a lower alkyl substituted amino group, and a lower alkyl substituted acylamino group. It is a phenyl group which has one or more substituents chosen from the group which consists of. In the case where the phenyl group has two or more substituents, at least one of the substituents is preferably a sulfo group, a carboxy group or a lower alkoxy group having a sulfo group. The other substituent is a sulfo group, a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group having a sulfo group, a carboxyl group, a chloro group, a bromo group, a nitro group, an amino group, a lower alkyl substituted amino group, or a lower alkyl substituted acylamino group. Is preferably. Other substituents are more preferably sulfo group, hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, carboxyl group, sulfoethoxy group, sulfopropoxy group, sulfobutoxy group, chloro group, nitro group, Amino group, N, N-dimethylamino group, N, N-diethylamino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, acetylamino group, propionamide group, butylamide group and the like. Especially preferably, they are a sulfo group, a carboxy group, a hydrogen atom, a methyl group, a methoxy group, a sulfoethoxy group, a sulfopropoxy group, or a sulfobutoxy group. The substitution position is not particularly limited, but preferably 2-position only, 4-position only, 2-position and 6-position combination, 2-position and 4-position combination, 3-position and 5-position Combinations are preferred, particularly preferably 2-position only, 4-position only, a combination of 2-position and 4-position, or a combination of 3-position and 5-position. In addition, only 2-position and only 4-position means having one substituent other than a hydrogen atom in 2-position or 4-position only.

The phenyl group having a substituent is preferably represented by the following formula (2).

[Formula 7]

One of R ₇ and R ₈ is a lower alkoxy group having a sulfo group, a carboxyl group, or a sulfo group, and the other is a lower alkoxy group having a hydrogen atom, a sulfo group, a carboxyl group, a sulfo group, a lower alkyl group, a lower alkoxy group, or a halogen group. , A nitro group, an amino group, a lower alkyl substituted amino group, or a lower alkyl substituted acylamino group. Preferably, one of R ₇ and R ₈ is a sulfo group or a carboxy group, and the other is a hydrogen atom, a sulfo group, a carboxy group, a methyl group, or a methoxy group.

The naphthyl group which may have a substituent is preferably a naphthyl group which may have one or more substituents selected from the group consisting of a hydroxyl group, a lower alkoxy group having a sulfo group, and a sulfo group.

The naphthyl group which may have a substituent, Preferably, it is the naphthyl group shown by following formula (3).

[Formula 8]

R ₉ is a hydrogen atom, a hydroxyl group, a lower alkoxy group having a sulfo group, or a sulfo group. n is an integer of 1-3. You may have the position of a sulfo group in the benzene nucleus of a naphthalene ring. Preferably, R ₉ is a hydrogen atom and n is 2. As a lower alkoxy group which has a sulfo group, a linear alkoxy group is preferable, and the substitution position of a sulfo group has the preferable alkoxy group terminal. The lower alkoxy group having a sulfo group is more preferably 3-sulfopropoxy group and 4-sulfobutoxy group. Although the position of the substituent which a naphthyl group has is not specifically limited, When it demonstrates by the number shown by Formula (3), when there are two substituents, the combination of 5-position and 7-position, or 6-position and 8-position is preferable. In the case of 3 substituents, 3-position, 5-position, 7-position, 3-position, 6-position, and 8-position are preferable.

Although R <_1> -R <_6> is not specifically limited, Preferably, they are each independently a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group which has a sulfo group, a carboxy group, a hydroxyl group, a halogen group, or lower alkyl substituted acyl It is an amino group. R ₁ to R ₆ are each independently, preferably a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group having a sulfo group, or a halogen group, and more preferably a hydrogen atom, a methyl group, an ethyl group, or a methoxy group , Ethoxy group, chloro group, fluorine group, 3-sulfopropoxy group or 4-sulfobutoxy group, More preferably, it is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or a 3-sulfopropoxy group to be.

In one embodiment, at least one of R ₁ to R ₆ is a lower alkoxy group having a sulfo group.

The lower alkoxy group having a sulfo group is preferably a C2-4 alkoxy group, more preferably a C3-4 alkoxy group, and particularly preferably a C3 alkoxy group. Although the substitution position of a sulfo group is not specifically limited, Preferably it is the terminal of an alkoxy group. The C 1-4 alkoxy group having a particularly preferable sulfo group is a 3-sulfopropoxy group and a 4-sulfobutoxy group, and most preferably a 3-sulfopropoxy group.

R ₁ is lower alkoxy contribution having a sulfo group, R ₃ is lower alkoxy contribution having a sulfo group, R ₅ is lower alkoxy contribution having sulfo, R ₁ and R ₃ is a lower alkoxy having a sulfo group, each independently It may also contribute, R ₁ and R ₅ may each independently be a lower alkoxy group having a sulfo group, R ₃ and R ₅ may each independently be a lower alkoxy group having a sulfo group, and R ₁ , R ₃ and R ₅ are each independently May be a lower alkoxy group having a sulfo group.

In one embodiment, all of R ₁ to R ₆ are not C 1-4 alkoxy groups having a sulfo group.

As the position of R ₁ to R ₆ , preferably, only 2-position, 5-position only, a combination of 2-position and 6-position, a combination of 2-position and 5-position, 3-position and 5- A combination of positions is preferred, more preferably a 2-position only, 5-position only, a combination of 2-position and 5-position. In addition, only 2-position and 5-position only means having one substituent other than a hydrogen atom in 2-position or 5-position only.

In one embodiment, A ¹ and A ² each independently have a naphthyl group or a substituent which may have a substituent selected from the group consisting of a hydroxyl group, a C 1-4 alkoxy group having a sulfo group, and a sulfo group. Except that when both A ¹ and A ² are a phenyl group having a substituent,

R ₁ to R ₆ each independently represent a hydrogen atom, a C 1-4 alkyl group, a C 1-4 alkoxy group, a C 1-4 alkoxy group having a sulfo group, a carboxyl group, a hydroxyl group, a halogen group, or a C 1-4 alkyl substituted acylamino group to be.

In one aspect, A ¹ and A ² are each independently a phenyl group which may have a substituent,

R ₁ to R ₆ are each independently a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxy group, a halogen group, or a C1-4 alkyl substituted acylamino group.

In one aspect, A ¹ and A ² are each independently a phenyl group which may have a substituent,

At least one of R ₁ to R ₆ is a C 1-4 alkoxy group having a sulfo group, and the rest are each independently a hydrogen atom, a C 1-4 alkyl group, a C 1-4 alkoxy group, a carboxyl group, a hydroxyl group, a halogen group, or It is a C1-4 alkyl substituted acylamino group.

It is preferable that the azo compound represented by Formula (1) is represented by following formula (4).

[Formula 9]

In one aspect, it is preferable that the azo compound represented by Formula (1) is represented by Formula (5).

[Formula 10]

At least 1 of R <_10> -R <_13> is a sulfo group, and otherwise, represents a C1-4 alkoxy group, methyl group, or methoxy group which has a hydrogen atom, a sulfo group, a carboxyl group, and a sulfo group.

R ₁ to R ₆ are as defined in formula (1).

Next, the specific example of the azo compound represented by Formula (1) is given to the following. In addition, the sulfo group, a carboxy group, and a hydroxyl group in a formula are represented by the form of a free acid.

Specific examples in which at least one of A ¹ and A ² are naphthyl groups are given below.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

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Formula 123]

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Formula 127]

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Formula 168

[Formula 169]

[Formula 170]

The specific example of both A <^1> and A <^2> being a phenyl group and R <_1> -R < ₆ > is not a lower alkoxy group which has a sulfo group is given to the following.

[Formula 171]

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Formula 263

Formula 264

[Formula 265]

[Formula 266]

[Formula 267]

[Formula 268]

[Formula 269]

[Formula 270]

[Formula 271]

[Formula 272]

[Formula 273]

[Formula 274]

[Formula 275]

[Formula 276]

[Formula 277]

[Formula 278]

[Formula 279]

[Formula 280]

[Formula 281]

[Formula 282]

[Formula 283]

[Formula 284]

[Formula 285]

[Formula 286]

[Formula 287]

[Formula 288]

[Formula 289]

Formula 290

[Formula 291]

[Formula 292]

[Formula 293]

[Formula 294]

[Formula 295]

[Formula 296]

[Formula 297]

[Formula 298]

[Formula 299]

[Formula 300]

[Formula 301]

[Formula 302]

Formula 303

[Formula 304]

[Formula 305]

Formula 306]

[Formula 307]

[Formula 308]

[Formula 309]

[Formula 310]

[Formula 311]

[Formula 312]

Formula 313

Formula 314

Formula 315

[Formula 316]

Formula 317

Formula 318

Specific examples in which both A ¹ and A ² are phenyl groups and at least one of R ₁ to R ₆ are lower alkoxy groups having a sulfo group are given below.

[Formula 319]

[Formula 320]

Formula 321

Formula 322

Formula 323

Formula 324

Formula 325

Formula 326

Formula 327

[Formula 328]

[Formula 329]

Formula 330

Formula 331

Formula 332

[333]

Formula 334

[Formula 335]

Formula 336

[Formula 337]

[Formula 338]

[Formula 339]

[Formula 340]

[Formula 341]

Formula 342

[Formula 343]

Formula 344

[Formula 345]

[346]

[Formula 347]

Formula 348

[Formula 349]

[Formula 350]

Formula 351

Formula 352

[Formula 353]

Formula 354

Formula 355

[Formula 356]

[Formula 357]

Formula 358

[Formula 359]

[Formula 360]

[Formula 361]

[Formula 362]

[Formula 363]

[Formula 364]

[Formula 365]

[Formula 366]

[Formula 367]

[Formula 368]

[Formula 369]

[Formula 370]

[Formula 371]

Formula 372

[Formula 373]

Formula 374

Formula 375

[Formula 376]

[Formula 377]

[Formula 378]

[Formula 379]

[Formula 380]

[Formula 381]

[Formula 382]

[Formula 383]

[Formula 384]

[Formula 385]

[Formula 386]

[Formula 387]

[Formula 388]

[Formula 389]

[Formula 390]

[Formula 391]

[Formula 392]

[Formula 393]

[Formula 394]

[Formula 395]

[Formula 396]

[Formula 397]

[Formula 398]

[Formula 399]

[Formula 400]

[Formula 401]

Formula 402

[Formula 403]

[Formula 404]

Formula 405

[Formula 406]

Formula 407

Formula 408

[Formula 409]

[Formula 410]

[Formula 411]

Formula 412

Formula 413

Formula 414

Formula 415

Formula 416

Formula 417

Formula 418

[Formula 419]

Formula 420

[Formula 421]

Formula 422

[Formula 423]

Formula 424

Formula 425

[Formula 426]

[Formula 427]

Formula 428

[Formula 429]

Formula 430

Formula 431

[Formula 432]

[Formula 433]

[Formula 434]

Formula 435

[Formula 436]

[Formula 437]

Formula 438

[Formula 439]

Formula 440

[Formula 441]

[Formula 442]

[Formula 443]

Formula 444

Formula 445

Formula 446

[Formula 447]

[Formula 448]

Formula 449

[Formula 450]

Formula 451

Formula 452

[Formula 453]

Formula 454

Formula 455

Formula 456

[Formula 457]

[Formula 458]

[Formula 459]

Formula 460

[Formula 461]

Formula 462

[Formula 463]

Formula 464

Formula 465

[Formula 466]

[Formula 467]

[Formula 468]

[469]

[470]

Formula 471

[Formula 472]

[Formula 473]

[474]

Formula 475

The azo compound represented by Formula (1) may be in the form of a free acid or in the form of a salt. Such salts include alkali salts such as lithium salts, sodium salts, and potassium salts, organic salts such as ammonium salts, and amine salts, and are preferably sodium salts.

The azo compound represented by Formula (1) or its salt is subjected to diazotization and coupling according to the manufacturing method of the usual azo dye as described in the nonpatent literature 1, and the urea as described in the patent document 3 It can be prepared by reacting with a topical agent.

As an example of a specific manufacturing method, the aniline which has a substituent as shown by following formula (i) is diazotized by the manufacturing method similar to the nonpatent literature 1, and it couples with the aniline of following formula (ii), and is a following formula The monoazoamino compound represented by (iii) is obtained.

[Formula 476]

(In formula, A <^1> represents the same meaning as the thing in said Formula (1).)

[Formula 477]

(In formula, R <_1> and R <_2> represents the same meaning as the thing in said Formula (1).)

[Formula 478]

(In formula, A <^1> , R <_1> and R <_2> represent the same meaning as the thing in said Formula (1).)

Subsequently, this monoazoamino compound (iii) is diazotized, and it is secondary-coupled with the aniline of following formula (iv), and the disazoamino compound represented by following formula (v) is obtained.

[Formula 479]

(In formula, R <_3> and R <_4> represents the same meaning as the thing in said Formula (1).)

[480]

(In formula, A <^1> and R <_1> -R <_4> represents the same meaning as the thing in said Formula (1).)

Similarly, the aniline which has a substituent represented by following formula (vi) is diazotized by the method similar to the nonpatent literature 1, couples with the aniline of following formula (vii), and is represented by the monoazo represented by following formula (viii) Obtain an amino compound.

[Formula 481]

(In formula, A <^2> represents the same meaning as the thing in said Formula (1).)

[Formula 482]

(In formula, R <_5> and R <_6> represents the same meaning as the thing in said Formula (1).)

[Formula 483]

(In formula, A <^2> , R <_5> and R <_6> represent the same meaning as the thing in said Formula (1).)

The azo compound of Formula (1) is obtained by making a disazoamino compound (v) and a monoazoamino compound (viii) react with ureide agents, such as chloroformate.

The diazotization step is, for example, by the method of mixing nitrites such as sodium nitrite with an aqueous solution or suspension of hydrochloric acid or sulfuric acid of the diazo component, or neutral or weakly alkaline of the diazo component. Nitrite is added to aqueous solution, and it carries out by the reverse method of mixing this and a photo acid. As for the temperature of diazotization, -10-40 degreeC is suitable. Moreover, it is preferable that the coupling process with aniline mixes acidic aqueous solutions, such as hydrochloric acid and an acetic acid, and each said diazo liquid, and is carried out in acidic conditions of pH 2-7 at -10-40 degreeC.

The disazoamino compound (v) and the monoazoamino compound (viii) obtained by coupling may be precipitated by calcite or salting out and filtered off, or may proceed to the next step while remaining in solution or suspension. When the diazonium salt is a poorly soluble suspension, it can be filtered and used in the following coupling process as a press cake.

Specific conditions of the ureidation reaction using the ureaization agent of the disazoamino compound (v) and the monoazoamino compound (viii) are 10 degrees by the manufacturing method shown on page 57 of patent document 3, for example. -90 degreeC and pH 3-11 are preferable, More preferably, it is 20-80 degreeC, pH 4-10, Especially preferably, it is 20-70 degreeC and pH 6-9. As ureate agent, in addition to chloro formate, phosgene, a triphosgene, ethyl chloroformate, chloro formate, butyl isoformate, chloro formate 4-nitrophenyl, chloro formate 4-fluorophenyl, chloro formate 4-chlorophenyl , Chloroformate 4-bromophenyl, diphenyl carbonate, bis (2-methoxyphenyl), bis (pentafluorophenyl), bis (4-nitrophenyl), and 1,1'-carbonyldi Imidazoles can be used but are not limited to these. The ureate agent is preferably chloroformate, chloroformate 4-nitrophenyl, chloroformate 4-chlorophenyl, diphenyl carbonate, bis (4-nitrophenyl), more preferably chloroformate, Chloroformate 4-nitrophenyl.

After completion of the uraidation reaction, the obtained azo compound of formula (1) is precipitated by salting out, filtered and taken out. When purification is necessary, salting out may be repeated or it may precipitate from water using an organic solvent. As an organic solvent used for purification, water-soluble organic solvents, such as alcohol, such as methanol and ethanol, and ketones, such as acetone, are mentioned, for example.

The aromatic amines represented by A ₁ -NH ₂ and A ₂ -NH _{2 which} are starting materials for synthesizing the azo compound represented by the formula (1) are naphthylamines or anilines.

As naphthylamine, it is preferable to use naphthylamine which has one or more selected from the group which consists of a hydrogen atom, a hydroxyl group, a sulfo group, and a sulfo group. Examples of naphthylamines include 4-aminonaphthalenesulfonic acid, 7-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid, 7-aminonaphthalene-1, 3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,5-disulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, etc. are mentioned. 7-aminonaphthalene-3-sulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,4-disulfonic acid, 7-aminonaphthalene-1,5-disulfonic acid, 2-amino-8 -Hydroxy-naphthalene-6-sulfonic acid, 3-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-aminonaphthalene-3,6,8-trisulfonic acid, 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid, 1-aminonaphthalene-3, 8-disulfonic acid, and the like are preferable.

As naphthylamine which has a sulfo group and the lower alkoxy group which has a sulfo group, for example, 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-sulfoprop Foxy) naphthalene-1,7-disulfonic acid, 6-amino-4- (3-sulfopropoxy) naphthalene-2,7-disulfonic acid, 7-amino-3- (3-sulfopropoxy) naphthalene- 1, 5- disulfonic acid, etc. are mentioned.

As aniline, 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 4-aminobenzoic acid, 2-amino-5-methylbenzenesulfonic acid, 2-amino-5-ethylbenzenesulfonic acid, 2- Amino-5-propylbenzenesulfonic acid, 2-amino-5-butylbenzenesulfonic acid, 4-amino-3-methylbenzenesulfonic acid, 4-amino-3-ethylbenzenesulfonic acid, 4-amino-3-propylbenzenesulfonic acid, 4- Amino-3-butylbenzenesulfonic acid, 2-amino-5-methoxybenzenesulfonic acid, 2-amino-5-ethoxybenzenesulfonic acid, 2-amino-5-propoxybenzenesulfonic acid, 2-amino-5-butoxybenzene Sulfonic acid, 4-amino-3-methoxybenzenesulfonic acid, 4-amino-3-ethoxybenzenesulfonic acid, 4-amino-3-propoxybenzenesulfonic acid, 4-amino-3-butoxybenzenesulfonic acid, 2-amino- 4-Sulfobenzoic acid, 2-amino-5-sulfobenzoic acid, 4-amino-3-sulfobenzoic acid, 5-amino-2-chlorobenzoic acid, 5-aminoisophthalic acid, 2-amino-5-chlorobenzenesulfonic acid, 2- Amino-5-bromobenzenesulfonic acid, 2-amino -5-nitrobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 2-amino-5-dimethylaminobenzenesulfonic acid, 2-amino-5-diethylaminobenzenesulfonic acid, 5-acetamide-2-aminobenzenesulfonic acid, 4-aminobenzene-1,3-disulfonic acid, 2-aminobenzene-1,4-disulfonic acid, 4-amino-2-methylbenzenesulfonic acid, 2- (4-aminophenoxy) ethane-1-sulfonic acid, 3 -(4-aminophenoxy) propane-1-sulfonic acid, 4- (4-aminophenoxy) butane-1-sulfonic acid, 2- (3-aminophenoxy) ethane-1-sulfonic acid, 3- (3-amino Phenoxy) propane-1-sulfonic acid, 4- (3-aminophenoxy) butane-1-sulfonic acid, 2-amino-5- (2-sulfoethoxy) benzenesulfonic acid, 2-amino-5- (3-sulfate Poppropoxy) benzenesulfonic acid, 2-amino-5- (4-sulfobutoxy) benzenesulfonic acid, 2-amino-5- (2-sulfoethoxy) benzoic acid, 2-amino-5- (3-sulfoprop Foxy) benzoic acid, 2-amino-5- (4-sulfobutoxy) benzoic acid, 4-amino-3- (2-sulfoethoxy) benzenesulfonic acid, 4-amino-3- (3-sulfopropoxy) benzene Sulfonic acid, 4-amino-3- (4-sulfur Butoxy) benzenesulfonic acid, 4-amino-3- (2-sulfoethoxy) benzoic acid, 4-amino-3- (3-sulfopropoxy) benzoic acid, 4-amino-3- (4-sulfobutoxy) Benzoic acid, 2- (4-amino-3-methylphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3-methylphenoxy) propane-1-sulfonic acid, 4- (4-amino-3-methyl Phenoxy) butane-1-sulfonic acid, 2- (4-amino-3-ethylphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3-ethylphenoxy) propane-1-sulfonic acid, 4- ( 4-Amino-3-ethylphenoxy) butane-1-sulfonic acid, 2- (4-amino-3-propylphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3-propylphenoxy) propane- 1-sulfonic acid, 4- (4-amino-3-propylphenoxy) butane-1-sulfonic acid, 2- (4-amino-3-butylphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3 -Butylphenoxy) propane-1-sulfonic acid, 4- (4-amino-3-butylphenoxy) butane-1-sulfonic acid, 2- (4-amino-3-methoxyphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3-methoxyphenoxy) propane-1-sulfonic acid, 4- (4-amino-3-methoxyphenoxy) butane-1-sulfonic acid, 2- (4-a Mino-3-ethoxyphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3-ethoxyphenoxy) propane-1-sulfonic acid, 4- (4-amino-3-ethoxyphenoxy) butane -1-sulfonic acid, 2- (4-amino-3-propoxyphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3-propoxyphenoxy) propane-1-sulfonic acid, 4- (4- Amino-3-propoxyphenoxy) butane-1-sulfonic acid, 2- (4-amino-3-butoxyphenoxy) ethane-1-sulfonic acid, 3- (4-amino-3-butoxyphenoxy) propane -1-sulfonic acid, 4- (4-amino-3-butoxyphenoxy) butane-1-sulfonic acid, and the like. The amino group may be protected by these aromatic amines. As a protecting group, an ω-methanesulfone group is mentioned, for example.

As aromatic amines (ii), (iv), and (vii) which are primary and secondary couplers, aniline, 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 3-methylaniline, 3-ethylaniline, 3-propylaniline, 3-butylaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-propoxyaniline, 2- Butoxyaniline, 3-methoxyaniline, 3-ethoxyaniline, 3-propoxyaniline, 3-butoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5- Dimethylaniline, 2,6-dimethylaniline, 3,5-dimethoxyaniline, 5-chloro-2-methoxyaniline, 5-chloro-2-ethoxyaniline, 5-chloro-2-propoxyaniline, 5- Chloro-2-butoxyaniline, 5-fluoro-2-methoxyaniline, 5-fluoro-2-ethoxyaniline, 5-fluoro-2-propoxyaniline, 5-fluoro-2-butoxy Aniline, 3-amino-4-methoxybenzoic acid, 3-amino-4-ethoxybenzoic acid, 3-amino-4-propoxybene Acids, 3-amino-4-butoxybenzoic acid, 2-aminophenol, 2-amino-4-methylphenol, 3-amino-4-methoxy-acetanilide, 3-amino-4-ethoxy-acetanilide, 3-Amino-4-propoxy-acetanilide, 3-amino-4-butoxy-acetanilide, 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, 3- (2-aminophenoxy Propane-1-sulfonic acid, 4- (2-amino-4-methylphenoxy) butane-1-sulfonic acid, 4- (2-aminophenoxy) butane-1-sulfonic acid, 2- (2-amino-4 -Methylphenoxy) ethane-1-sulfonic acid, 2- (2-aminophenoxy) ethane-1-sulfonic acid, 3- (3-amino-4-methylphenoxy) propane-1-sulfonic acid, 3- (3- Aminophenoxy) propane-1-sulfonic acid, 4- (3-amino-4-methylphenoxy) butane-1-sulfonic acid, 4- (3-aminophenoxy) butane-1-sulfonic acid, 2- (3-amino -4-methylphenoxy) ethane-1-sulfonic acid, 2- (3-aminophenoxy) ethane-1-sulfonic acid, 3- (2-amino-4-methoxyphenoxy) propane-1-sulfonic acid, 4- (2-amino-4-methoxyphenoxy) butane-1-sulfonic acid, 2- (2-ami 4-methoxyphenoxy) ethane-1-sulfonic acid, 3- (3-amino-4-methoxyphenoxy) propane-1-sulfonic acid, 4- (3-amino-4-methoxyphenoxy) butane- 1-sulfonic acid, 2- (3-amino-4-methoxyphenoxy) ethane-1-sulfonic acid, 3- (2-amino-4-ethoxyphenoxy) propane-1-sulfonic acid, 4- (2-amino 4-ethoxyphenoxy) butane-1-sulfonic acid, 2- (2-amino-4-ethoxyphenoxy) ethane-1-sulfonic acid, 3- (3-amino-4-ethoxyphenoxy) propane- 1-sulfonic acid, 4- (3-amino-4-ethoxyphenoxy) butane-1-sulfonic acid, 2- (3-amino-4-ethoxyphenoxy) ethane-1-sulfonic acid, 3- (2-amino 4-chlorophenoxy) propane-1-sulfonic acid, 3- (2-amino-4-fluorophenoxy) propane-1-sulfonic acid, 4- (2-amino-4-chlorophenoxy) butane-1- Sulfonic acid, 4- (2-amino-4-fluorophenoxy) butane-1-sulfonic acid, 2- (2-amino-4-chlorophenoxy) ethane-1-sulfonic acid, and 2- (2-amino-4 -Fluorophenoxy) ethane-1-sulfonic acid, etc. are mentioned. The amino group may be protected by these aromatic amines. As a protecting group, an ω-methanesulfone group is mentioned, for example.

<Dye-based polarizing film>

A dye type polarizing film contains the polarizing film base material containing the azo compound represented by Formula (1) or its salt as a dichroic dye. The dye-based polarizing film may be either a neutral gray polarizing film or a color polarizing film, and is preferably a neutral gray polarizing film. Here, "neutral gray" is the light leakage of the specific wavelength in the wavelength range of a visible light region in the state which superimposed two polarizing films so that the orientation direction may mutually cross (henceforth "orthogonal position.") Color leakage).

The dye-based polarizing film contains one kind or a combination of plural kinds of azo compounds represented by the formula (1) or salts thereof as a dichroic dye, and may further contain one or more kinds of other organic dyes as necessary. . The other organic dye is not particularly limited, but is preferably a dichroic dye having a water absorption characteristic in a wavelength region different from the absorption wavelength region of the azo compound or salt thereof represented by the formula (1). As other organic dye, for example, C.I.direct. Yellow 12, C.I.Direct. Yellow 28, C.I.direct. Yellow 44, C.I.direct. Orange 26, C.I.Direct. Orange 39, C.I.Direct. Orange 71, C.I.Direct. Orange 107, C.I.Direct. Red 2, C.I.direct. Red 31, C. I. Direct. Red 79, C. I. Direct. Red 81, C.I.direct. Red 247, C.I.direct. Green 80 and C.I.Direct. Although green 59 and dyes of patent documents 1-6 are mentioned as a typical example, It is preferable to use the dye developed for polarizing plates as described in patent documents 1-6 according to the objective. These organic dyes are used as salts of free acids, alkali metal salts (eg, Na salts, K salts, Li salts), ammonium salts, or amines.

When using together other organic dye, the kind of organic dye mix | blended is different depending on whether the target polarizing film is a neutral gray polarizing film, the color polarizing film for liquid crystal projectors, or another color polarizing film. Although the compounding ratio is not specifically limited, Generally, using the sum total of at least 1 or more types of other organic dye in 0.01-100 mass parts with respect to 1 mass part of azo compounds or its salt of Formula (1). Preferably, the range of 0.1-10 mass parts is more preferable.

When the target polarizing film is a neutral gray polarizing film, the kind and compounding ratio of the other organic dye used together are adjusted so that color leakage in the wavelength range of the visible light region of the polarizing film obtained may become small.

When the target polarizing film is a color polarizing film, it has a high single-plate average light transmittance in the specific wavelength range of the polarizing film obtained, and for example, the single-plate 39% or more in a specific wavelength range so that the average light transmittance of a quadrature may become low. The kind and compounding ratio of the other organic dye used together are adjusted so that it may have an average light transmittance and the average light transmittance of 0.4% or less orthogonal cross.

Dye-type polarizing film contains the azo compound represented by Formula (1) or its salt, and dichroic dye containing other dye as needed by a well-known method in a polarizing film base material (for example, a polymer film), and orientating it. It can manufacture by making it, making it mix with a liquid crystal, or aligning by a coating method.

The polarizing film base material is preferably a polymer film, and more preferably a film made of a polyvinyl alcohol resin or a derivative thereof. Specific examples of the polarizing film base material include polyvinyl alcohol resins or derivatives thereof, and those modified with olefins such as ethylene and propylene, unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, and maleic acid, and the like. Can be mentioned. As a polarizing film base material, the film which consists of polyvinyl alcohol resin or its derivative (s) is used suitably from the point of adsorption and orientation of dye. The thickness of a polarizing film base material is 10-100 micrometers normally, Preferably it is about 20-80 micrometers.

When a polarizing film base material is a polymer film, in order to contain the azo compound or its salt of Formula (1), the method of dyeing a polymer film is employ | adopted normally. Dyeing is performed as follows, for example. First, the azo compound represented by Formula (1) or its salt, and other organic dye are dissolved in water as needed, and the salt bath is prepared. Although the dye concentration in a salt bath is not specifically limited, Usually, it selects in about 0.001-10 mass%. Moreover, you may use a dyeing adjuvant as needed, For example, it is suitable to use forget-me-not at the density | concentration of about 0.1-10 mass%, for example. In this way, a polymeric film can be immersed in the prepared salt bath for 1 to 10 minutes, and dyeing can be performed. Dyeing temperature becomes like this. Preferably it is about 30-80 degreeC.

The orientation of the azo compound or its salt represented by Formula (1) is performed by extending | stretching the polymeric film dyed with dichroic dye. Although drawing ratio is 2-8 times generally applied, it is not limited, Preferably it is 3-7.5 times, More preferably, 4-7 times is applied. As a method of extending | stretching, you may use any well-known method, such as a wet method and a dry method, for example. You may perform extending | stretching of a polymer film before dyeing as needed. In this case, the water-soluble dye is oriented at the time of dyeing. The polymer film containing and aligning the water-soluble dye is subjected to post-treatment such as boric acid treatment by a known method as necessary. Such post-processing is performed for the purpose of improving the light transmittance and polarization degree of a polarizing film. The conditions of the boric acid treatment vary depending on the kind of the polymer film to be used and the kind of the dye to be used. Generally, the boric acid concentration of the boric acid aqueous solution is, for example, 0.1 to 15% by mass, preferably 1 to 10% by mass. It is set as the range, and processing is performed by immersing for 0.5 to 10 minutes in the temperature range of 30-80 degreeC, Preferably it is 40-75 degreeC. In addition, you may perform fix process simultaneously with the aqueous solution containing a cation type high molecular compound as needed.

Examples of the use of the dye-based polarizing film include liquid crystal projectors, electronic desk calculators, watches, notebook personal computers, word processors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments and indicators, and lenses and glasses. . The dye polarizing film has a high polarization performance comparable to the polarizing film using iodine and is also excellent in durability. For this reason, it is especially suitable for various liquid crystal displays and liquid crystal projectors, such as the use which requires high polarization performance and durability, for example, for a vehicle installation and outdoor display (for example, the display use of industrial instruments, or a wearable use). Do.

<Dye-based polarizing plate>

A dye-based polarizing plate can be obtained by bonding a transparent protective film to one side or both sides of a dye-based polarizing film. Since a dye type polarizing plate is equipped with said dye type polarizing film, it has the outstanding polarization performance and moisture resistance, heat resistance, and light resistance. As a material which forms a transparent protective film, the material excellent in optical transparency and mechanical strength is preferable, For example, fluorine-type films, such as a cellulose acetate film, an acryl-type film, a tetrafluoroethylene / hexafluoropropylene copolymer, polyester The film etc. which consist of resin, polyolefin resin, or polyamide resin are used. The transparent protective film is preferably a triacetyl cellulose (TAC) film or a cycloolefin-based film. It is preferable that the thickness of a protective film is 40-200 micrometers normally.

Examples of the adhesive that can be used to bond the dye-based polarizing film and the protective film include polyvinyl alcohol adhesives, urethane emulsion adhesives, acrylic adhesives, polyester isocyanate adhesives, and the like. Suitable.

You may further form a transparent protective layer on the surface of a dye type polarizing plate. As an additional transparent protective layer, an acryl-type, polysiloxane-type hard-coat layer, a urethane type protective layer, etc. are mentioned, for example. Moreover, in order to improve single-sheet light transmittance further, it is preferable to form AR layer (antireflection layer) on this transparent protective layer. The AR layer can be formed, for example, by vapor deposition or sputtering of a material such as silicon dioxide or titanium oxide, and can be formed by thinly applying a fluorine-based material. It is preferable that a dye type polarizing plate further includes a support body. The dye-based polarizing plate affixes a retardation plate on the surface, and can also be used as an elliptically polarizing plate.

The dye-based polarizing plate may be one of a neutral gray polarizing plate and a color polarizing plate depending on the application.

Since neutral gray polarizing plate has neutral color, there is little color leakage of orthogonal position in the polarization region of visible light region, it is excellent in polarization performance, the fall of discoloration and polarization performance is suppressed even in high temperature, high humidity state, and durability is high, Suitable for vehicle, vehicle or outdoor display.

The neutral gray polarizing plate for vehicle or outdoor display is preferably a polarizing plate having an AR layer formed on the polarizing plate composed of a dye-based polarizing film and a transparent protective film in order to further improve the single light transmittance. And the polarizing plate with AR layer and support body which stuck both of AR layer and support bodies, such as transparent resin, is more preferable. The AR layer can be formed on one side or both sides of the polarizing plate. The support is preferably formed on one side of the polarizing plate, and may be formed directly on the polarizing plate, or a polarizing plate (AR layer / polarizing plate / AR layer) having an AR layer formed on the support may be formed. It is preferable that the polarizing plate with AR layer and support body is equipped with AR layer / polarizing plate / AR layer / support in this order. It is preferable that a support body has a flat part for affixing a polarizing plate, and since it is an optical use, it is preferable that it is a transparent substrate. As the transparent substrate, there are broadly divided inorganic substrates and organic substrates, and inorganic substrates such as soda glass, borosilicate glass, quartz substrate, sapphire substrate, and spinel substrate, and acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and Although organic substrates, such as a cycloolefin polymer, are mentioned, an organic substrate is preferable. The thickness and the size of the transparent substrate may be a desired size.

Since a color polarizing plate is excellent in polarizing performance and does not cause discoloration and fall of polarization performance even in a high temperature, high humidity state, it is suitable for liquid crystal projectors, display devices, such as a vehicle installation and outdoor display.

The color polarizing plate for liquid crystal projectors has brightness and excellent polarization performance, and the required wavelength range of the polarizing plate (A. When an ultrahigh pressure mercury lamp is used; 420 to 500 nm for the blue channel, 500 to 580 nm for the green channel, and 600 for the red channel. -680 nm, B. Peak wavelength when a three-color LED lamp is used; single-plate average light transmittance in the blue channel 430-450 nm, the green channel 520-535 nm, and the red channel 620-635 nm) is 39%. As mentioned above, the average light transmittance of orthogonal position is 0.4% or less, More preferably, the single plate average light transmittance in the required wavelength range of the polarizing plate is 41% or more, and the average light transmittance of orthogonal position is 0.3% or less, More preferably, Is 0.2% or less. More preferably, the single plate average light transmittance in the required wavelength range of this polarizing plate is 42% or more, and the average light transmittance of orthogonal | orthogonal positions is 0.1% or less.

In addition, the single-plate average light transmittance is a light transmittance in the specific wavelength range when natural light is incident on one polarizing plate (henceforth simply called a "polarizing plate") which does not form support bodies, such as an AR layer and a transparent glass plate. Is the average value. The average light transmittance of the orthogonal position is an average value of the light transmittance in the specific wavelength range when natural light is incident in the state which superimposed two polarizing plates so that the orientation directions orthogonally crossed each other.

As for the polarizing film used for a vehicle-mounted or outdoor color display polarizing plate, like a neutral gray polarizing plate, the protective layer, AR layer, support body, etc. may be formed in the dye-type polarizing plate as needed. The color polarizing plate with a support body is obtained by apply | coating a transparent adhesive agent (adhesive) agent to a support body flat part, for example, and then sticking a dye type polarizing plate to this application surface. Alternatively, a transparent adhesive (adhesive) agent may be applied to the dye-based polarizing plate, and then the support may be attached to this coated surface. The adhesive (adhesive) agent is preferably, for example, an acrylate ester type. In addition, when using this dye type polarizing plate as an elliptical polarizing plate, it is common to affix the phase difference plate side to a support body, and to make the order of lamination | stacking of a dye type polarizing plate / phase difference plate / support body, but attaching the polarizing plate side to a support body and retarding plate / polarizing plate / It is good also as a lamination order of a support body.

<Liquid crystal display device>

A liquid crystal display device is provided with said dye type polarizing film or dye type polarizing plate. Liquid crystal display devices are, for example, for electronic desk calculators, watches, notebook personal computers, word processors, liquid crystal televisions, car navigation systems, and displays such as indoor and outdoor measuring instruments and indicators, and particularly require high polarization performance and durability. It is suitably used for various liquid crystal displays to be used, for example, for vehicle mounting or for outdoor display (for example, display use of industrial instruments and wearable use). It is suitable that the dye type polarizing film or dye type polarizing plate with which a liquid crystal display device is equipped is neutral gray.

In the liquid crystal display device, the dye-based polarizing plate is disposed on either or both of the incident side and the exit side of the liquid crystal cell. The dye-based polarizing plate may or may not be in contact with the liquid crystal cell, but is preferably not in contact from the viewpoint of durability. On the emission side of the liquid crystal cell, when the dye-based polarizing plate is in contact with the liquid crystal cell, the liquid crystal cell can be used as a support for the dye-based polarizing plate. When the dye-based polarizing plate is not in contact with the liquid crystal cell, it is preferable to use a dye-based polarizing plate on which a support body other than the liquid crystal cell is formed. In terms of durability, it is preferable that the dye-based polarizing plate is disposed on both the incidence side and the outgoing side of the liquid crystal cell, and it is preferable that the polarizing plate surface of the dye-based polarizing plate is disposed on the liquid crystal cell side and the support surface is placed on the light source side. desirable. In addition, the incident side of a liquid crystal cell means the light source side, and the opposite side is called an emission side.

It is preferable that the liquid crystal cell with which a liquid crystal display device is equipped is an active matrix type, for example, and is formed by enclosing a liquid crystal between the transparent substrate in which the electrode and TFT were formed, and the transparent substrate in which the counter electrode was formed. Light emitted from a light source such as a cold cathode tube lamp or a white LED passes through the dye-based polarizing plate, and then passes through the liquid crystal cell, the color filter, and the dye-based polarizing plate and is projected onto the display screen.

Since the dye-based polarizing plate has brightness, excellent polarization performance, polarization and light resistance, the liquid crystal display device does not easily cause discoloration and deterioration in polarization performance even at high temperature and high humidity, such as in a car or outdoors, and is highly reliable.

Example

EXAMPLES Hereinafter, although an Example demonstrates further in detail, these are illustrative and do not limit this invention at all. % And part in an example are a mass reference | standard unless there is particular notice.

Example E1: Synthesis of Azo Compounds of Formula (A-3)

30.3 parts of 7-aminonaphthalene-1,3-disulfonic acid was added to 500 parts of water, cooled to 31.3 parts of 35% hydrochloric acid at 10 ° C. or lower, and then 6.9 parts of sodium nitrite was added and stirred at 5 to 10 ° C. for 1 hour. To diazotize. 12.3 parts of 2-methoxyaniline were added there, stirring at 10-30 degreeC, sodium carbonate was added, it was made into pH 3, and it stirred further to complete a coupling reaction, and it filtered, and was represented by following formula (A-3M) 30.6 parts of monoazoamino compounds shown were obtained.

Formula 484

30.6 parts of the obtained monoazoamino compound is added to 400 parts of water, it melt | dissolves with sodium hydroxide, 21.9 parts of 35% hydrochloric acid are added at 10-30 degreeC, 4.8 parts of sodium nitrite are added next, and it stirred at 20-30 degreeC for 1 hour To diazotize. 17.2 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid are added there, stirring at 20-30 degreeC, sodium carbonate is added, it is pH 4, and also it stirred and coupling reaction Was completed, and it filtered and obtained 38.8 parts of disazoamino compounds represented by a following formula (A-3D).

Formula 485

24.5 parts of monoazoamino compound (A-3M) is added to 500 parts of water, it melt | dissolves with sodium hydroxide, 10.0 parts of phenyl chloroformates are added, it stirred at 30-50 degreeC for 2 hours, and then the disazoamino compound (A- 3D) 38.8 parts were added, and it stirred at 50-70 degreeC for 5 hours, and was uraidized. It salted with sodium chloride, filtered, and obtained 12.5 parts of urede compounds represented by said formula (A-3). The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 454 nm.

Example E2: Synthesis of Azo Compounds of Formula (A-6)

24.2 parts of 7-aminonaphthalene-1,3-disulfonic acid is added to 400 parts of water, cooled to 25.0 parts of 35% hydrochloric acid at 10 ° C. or lower, and then 5.5 parts of sodium nitrite are added and stirred at 5 to 10 ° C. for 1 hour. To diazotize. 8.6 parts of 2-methylanilines are added thereto, and sodium carbonate is added to pH 3 while stirring at 10 to 30 ° C, further stirring to complete the coupling reaction, followed by filtration and represented by the following formula (A-6MR). 23.6 parts of monoazoamino compound were obtained.

Formula 486

38.8 parts of disazoamino compound (A-3D) and 23.6 parts of monoazoamino compound (A-6MR) are added to 500 parts of water, dissolved with sodium hydroxide, 12.9 parts of 4-chloroformate 4-nitrophenyl are added, and 50 to 70 It stirred at 4 degreeC for 4 hours, and was ureated. It was salted with sodium chloride, and it filtered and obtained 12.2 parts of ureide compounds represented by said formula (A-6). The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 443 nm.

Example E3: Synthesis of Azo Compounds of Formula (A-19)

29.5 parts of monoazoamino compound (A-6MR) was added to 400 parts of water, dissolved with sodium hydroxide, 21.9 parts of 35% hydrochloric acid was added at 10 to 30 ° C, and then 4.8 parts of sodium nitrite was added thereto at 20 to 30 ° C. It stirred for 1 hour and diazotized. 17.2 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid are added there, stirring at 20-30 degreeC, sodium carbonate is added, it is pH 4, and also it stirred and coupling reaction Was completed, and it filtered and obtained 38.0 parts of disazoamino compounds represented by a following formula (A-19D).

[Formula 487]

38.0 parts of obtained disazoamino compound (A-19D) and 24.5 parts of monoazoamino compound (A-3M) are added to 500 parts of water, and it melt | dissolves with sodium hydroxide, and 12.9 parts of 4-chloro formate chloroform are added, 50- It stirred at 70 degreeC for 4 hours, and was uraidized. 9.4 parts of ureide compounds represented by the said Formula (A-19) were obtained by salting with sodium chloride and filtering. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 438 nm.

Example E4: Synthesis of Azo Compounds of Formula (A-20)

The same formula as in Example E3 except that 16.2 parts of 3- (2-aminophenoxy) propane-1-sulfonic acid was used instead of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid. 11.2 parts of ureide compounds represented by (A-20) were obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 430 nm.

Example E5: Synthesis of Azo Compounds of Formula (A-32)

In the same manner as in Example E1, except that 9.3 parts of aniline were used instead of 2-methoxyaniline as a raw material of the disazoamino compound (A-3D), 10.2 parts of the ureide compound represented by the formula (A-32) was obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 440 nm.

Example E6: Synthesis of Azo Compounds of Formula (A-36)

In the same manner as in Example E3 except for the use of 8.5 parts of 2,5-dimethylaniline in place of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid and represented by the formula (A-36) 9.0 parts of a raid compound were obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 416 nm.

Example E7: Synthesis of Azo Compounds of Formula (A-130)

11.0 parts of 4-aminobenzoic acid were added to 300 parts of water, cooled, 25.0 parts of 35% hydrochloric acid was added at 10 degrees C or less, Next, 5.5 parts of sodium nitrite were added, and it stirred at 5-10 degreeC for 1 hour, and diazotized. 11.0 parts of 2-methoxy-5-methylaniline were added there, stirring at 10-30 degreeC, sodium carbonate was added, it was made into pH 3, and further stirred, the coupling reaction was completed, it filtered, and the following formula (A 1130 parts of monoazoamino compound represented by -130MR) were obtained.

[Formula 488]

16.0 parts of the obtained monoazoamino compound (A-130MR) was added to 500 parts of water, dissolved with sodium hydroxide, and 10.0 parts of phenyl chloroformate were stirred at 30 to 50 ° C for 2 hours, followed by disazoamino compound (A-19D) 38.0 parts were added and uraided at 50-70 degreeC. It was salted out with sodium chloride, and it filtered and obtained 10.4 parts of ureide compounds represented by said formula (A-130). The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 441 nm.

Example E8 Synthesis of Azo Compounds of Formula (A-61)

25.3 parts of 4-aminobenzene-1,3-disulfonic acid are added to 500 parts of water, cooled, and 31.3 parts of 35% hydrochloric acid is added at 10 degrees C or less, Next, 6.9 parts of sodium nitrite are added, and it is 1 at 5-10 degreeC. It stirred for the time and diazotized. 12.1 parts of 2, 5- dimethylaniline are added there, stirring at 10-30 degreeC, sodium carbonate is added, it is made into pH3, and further stirred, the coupling reaction is completed, it filtered, and it is following formula (A- 27.0 parts of monoazoamino compounds represented by 61 ml) were obtained.

[Formula 489]

27.0 parts of the obtained monoazoamino compound was added to 400 parts of water, it melt | dissolves with sodium hydroxide, 25.0 parts of 35% hydrochloric acid are added at 10-30 degreeC, 5.5 parts of sodium nitrites are added next, and it stirred at 20-30 degreeC for 1 hour. To diazotize. 17.2 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid are added there, stirring at 20-30 degreeC, sodium carbonate is added, it is pH 4, and also it stirred and coupling reaction Was completed, and it filtered and obtained 35.9 parts of disazoamino compounds represented by a following formula (A-61D).

[490]

24.5 parts of monoazoamino compound (A-3M) are added to 500 parts of water, and it melt | dissolves with sodium hydroxide, and 10.0 parts of phenyl chloroformates are stirred at 30-50 degreeC for 4 hours, and the disazoamino compound (A-61D) 35.9 A part was added, it stirred at 50-70 degreeC for 5 hours, and was ureated. It was salted out with sodium chloride, and it filtered and obtained 12.1 parts of ureide compounds represented by said formula (A-61). The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 435 nm.

Example E9: Synthesis of Azo Compounds of Formula (A-92)

11.1 parts of ureide compounds represented by said formula (A-92) were obtained like Example E8 except having used 10.7 parts of 2-methylanilines instead of 2, 5- dimethyl aniline. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 435 nm.

Example E10: Synthesis of Azo Compounds of Formula (A-95)

The same formula as in Example E9, except that 16.2 parts of 3- (2-aminophenoxy) propane-1-sulfonic acid was used instead of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid. 12.7 parts of ureide compounds represented by (A-95) were obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 428 nm.

Example E11 Synthesis of Azo Compounds of Formula (A-99)

Except having used 16.2 parts of 3- (2-aminophenoxy) propane- 1-sulfonic acids instead of 2-methoxyaniline, 13.5 parts of ureide compounds represented by said Formula (A-99) were obtained like Example E9. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 434 nm.

Example E12 Synthesis of Azo Compounds of Formula (A-100)

In the same manner as in Example E9, except that 12.1 parts of 2-ethylaniline were used instead of 2-methyl aniline, 11.0 parts of the ureide compound represented by the formula (A-100) was obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 435 nm.

Example E13: Synthesis of Azo Compounds of Formula (B-17)

25.3 parts of 4-aminobenzene-1,3-disulfonic acid are added to 500 parts of water, cooled, and 31.3 parts of 35% hydrochloric acid is added at 10 degrees C or less, Next, 6.9 parts of sodium nitrite are added, and it is 1 at 5-10 degreeC. It stirred for the time and diazotized. 12.1 parts of 2, 5- dimethylaniline are added there, stirring at 10-30 degreeC, sodium carbonate is added and it is set as pH 3, and further stirred, the coupling reaction is completed, it filtered, and it is following formula (B- 30.8 parts of monoazoamino compounds represented by 17 ml) were obtained.

[Formula 491]

30.8 parts of obtained monoazoamino compounds are added to 400 parts of water, it melt | dissolves with sodium hydroxide, 25.0 parts of 35% hydrochloric acid are added at 10-30 degreeC, 5.5 parts of sodium nitrites are added next, and it stirred at 20-30 degreeC for 1 hour. To diazotize. 11.0 parts of 2-methoxy-5-methylaniline were added there, stirring at 20-30 degreeC, adding sodium carbonate to pH3, stirring further, completing a coupling reaction, and filtering, 34.1 parts of disazoamino compound represented by (B-17D) was obtained.

[Formula 492]

11.0 parts of 4-aminobenzoic acid were added to 250 parts of water, cooled, 25.3 parts of 35% hydrochloric acid was added at 10 degrees C or less, Next, 5.5 parts of sodium nitrite were added, and it stirred at 5-10 degreeC for 1 hour, and diazotized. . 11.0 parts of 2-methoxy-5-methylaniline are added there, stirring at 10-30 degreeC, adding sodium carbonate to pH3, stirring further, completing a coupling reaction, filtering, and the following formula 18.3 parts of monoazoamino compounds represented by (B-17MR) were obtained.

[Formula 493]

18.3 parts of the obtained monoazoamino compound (B-17MR) are added to 250 parts of water, dissolved with sodium hydroxide, 10.0 parts of phenyl chloroformate are added, stirred at 30 to 50 ° C for 4 hours, and then the disazoamino compound (B -17D) 34.1 parts were added, and it stirred at 50-70 degreeC for 5 hours, and was ureated. It was salted out with sodium chloride, and it filtered and obtained 10.5 parts of ureide compounds represented by said Formula (B-17). The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 435 nm.

Example E14: Synthesis of Azo Compounds of Formula (B-1)

In the same manner as in Example E13, except that 20.3 parts of 4-aminobenzene-1,3-disulfonic acid was used instead of 4-aminobenzoic acid, 12.0 parts of the ureide compound represented by the formula (B-1) was obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 427 nm.

Example E15: Synthesis of Azo Compounds of Formula (B-20)

In the same manner as in Example E13, except that 13.8 parts of 5-amino-2-chlorobenzoic acid were used instead of 4-aminobenzoic acid, 10.2 parts of the ureide compound represented by Formula (B-20) was obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 432 nm.

Example E16 Synthesis of Azo Compounds of Formula (B-29)

The same formula as in Example E14 except that 18.7 parts of 2-amino-5-methylbenzenesulfonic acid is used instead of 4-aminobenzene-1,3-disulfonic acid as a raw material of the disazoamino compound (B-17D). 10.1 parts of ureide compounds represented by (B-29) were obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 425 nm.

Example E17 Synthesis of Azo Compounds of Formula (B-48)

Except having used 10.7 parts of 2-methylanilines instead of 2, 5- dimethylaniline, 13.5 parts of ureide compounds represented by said Formula (B-48) were obtained like Example E13. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 433 nm.

Example E18: Synthesis of Azo Compounds of Formula (C-5)

30.8 parts of monoazoamino compound (B-17ML) is added to 400 parts of water, it melt | dissolves with sodium hydroxide, 25.0 parts of 35% hydrochloric acid is added at 10-30 degreeC, 5.5 parts of sodium nitrites are added next, 20-30 degreeC The mixture was stirred for 1 hour and diazotized. 19.6 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid are added there, stirring at 20-30 degreeC, adding sodium carbonate to pH 4, and also stirring and coupling reaction Was completed, and it filtered and obtained 41.0 parts of disazoamino compounds represented by following formula (C-5D).

[Formula 494]

15.0 parts of 2-amino-5-methylbenzenesulfonic acid are added to 250 parts of water, cooled, and 25.0 parts of 35% hydrochloric acid is added at 10 degrees C or less, Next, 5.8 parts of sodium nitrite are added and stirred at 5-10 degreeC for 1 hour. To diazotize. 11.0 parts of 2-methoxy-5-methylaniline are added there, stirring at 10-30 degreeC, adding sodium carbonate to pH3, stirring further, completing a coupling reaction, filtering, and the following formula 21.5 parts of monoazoamino compounds represented by (C-5MR) were obtained.

[Formula 495]

21.5 parts of obtained monoazoamino compound (C-5MR) are added to 500 parts of water, it melt | dissolves with sodium hydroxide, 10.0 parts of phenyl chloroformates are added, and it stirs at 30-50 degreeC for 2 hours, and then disazoamino compound (C -5D) 41.0 parts was added, and it stirred at 50-70 degreeC for 5 hours, and was ureated. It was salted out with sodium chloride, and it filtered and obtained 12.9 parts of urede compounds represented by said formula (C-5). The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 425 nm.

Example E19 Synthesis of Azo Compounds of Formula (C-16)

Except for using 11.0 parts of 4-aminobenzoic acid instead of 2-amino-5-methylbenzenesulfonic acid, 12.8 parts of ureide compounds represented by said Formula (C-16) were obtained like Example E18. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 437 nm.

Example E20: Synthesis of Azo Compounds of Formula (C-19)

In the same manner as in Example E18, except that 13.8 parts of 5-amino-2-chlorobenzoic acid were used instead of 2-amino-5-methylbenzenesulfonic acid, 13.5 parts of the ureide compound represented by the formula (C-19) was obtained. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 435 nm.

Example E21: Synthesis of Azo Compounds of Formula (C-46)

10.7 parts of 2-methylaniline was used instead of 2,5-dimethylaniline, and 19.7 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid was used instead of 2-methoxy-5-methylaniline. Except for the used point, it carried out similarly to Example E19, and obtained 13.1 parts of ureide compounds represented by said formula (C-46). The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 440 nm.

Example E22 Synthesis of Azo Compounds of Formula (C-49)

Using 10.7 parts of 2-methylaniline in place of 2,5-dimethylaniline and 21.3 parts of 3- (2-amino-4-chlorophenoxy) propane-1-sulfonic acid in place of 2-methoxy-5-methylaniline Except for the point, 13.7 parts of the ureide compound represented by the formula (C-49) was obtained in the same manner as in Example E19. The maximum absorption wavelength in the 20% pyridine aqueous solution of this compound was 438 nm.

(Examples F1-F22: manufacture of dye-based polarizing film)

Formulas (A-3), (A-6), (A-19), (A-20), (A-32), (A-36), and (A-130) obtained in Examples E1 to E22. , (A-61), (A-92), (A-95), (A-99), (A-100), (B-17), (B-1), (B-20), ( B-29), (B-48), (C-5), (C-16), (C-19), 0.03% of each azo compound of (C-46), (C-49) and forget-me-not A 75-micrometer-thick polyvinyl alcohol was immersed for 4 minutes in each 45 degreeC aqueous solution (salt bath) which made it the density | concentration of 0.1%. This film was extended | stretched 5 times at 50 degreeC in 3% boric-acid aqueous solution, water-washed and dried, maintaining the tension state, and the polarizing film was obtained.

Table 1 shows absorption wavelengths and the polarization ratios when the polarization ratios of the obtained dye-based polarizing films become maximum. As shown in Table 1, all the polarizing films manufactured using the compound of this invention had a high polarization ratio.

The measurement of the absorption wavelength and the calculation of the polarization rate when the polarization ratio becomes the maximum of the polarizing film are made using the parallel transmittance and the orthogonal transmittance at the time of polarization incidence measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.). Calculated.

Here, parallel transmittance (Ky) is a transmittance measured by setting the absorption axis of an absolute polarizer (polarizing plate of 99.99% of polarization degree) and the absorption axis of a polarizing film in parallel, and the orthogonal transmittance (Kz) is the absorption axis and polarization of an absolute polarizer. The transmittance | permeability measured by setting the absorption axis of a film orthogonally is shown.

Parallel transmittance and orthogonal transmittance of each wavelength were measured at 1 nm intervals at 380 to 780 nm. Using the value measured, respectively, the polarization rate of each wavelength was computed from following formula (I), and the highest polarization rate and absorption wavelength (nm) at that time were obtained in 380-780 nm.

Polarization rate (%) = [(Ky-Kz) / (Ky + Kz)] × 100 (I)

(Comparative Example 1: Manufacture of Polarizing Film)

A polarizing film was produced in the same manner as in Example F1 except that Sea Eye Direct Orange 39 was used instead of the compound of Formula (A-3).

(Comparative Example 2: Production of Polarizing Film)

A polarizing film was produced in the same manner as in Example F1 except that Sea Eye Direct Yellow 44 was used instead of the compound of Formula (A-3).

As one index indicating the quality of an image, there is a contrast indicating a difference between luminance in white display and black display. Table 2 shows the contrast in the maximum absorption wavelength of the dye-based polarizing films obtained in Examples F1 to F22 and Comparative Examples 1 and 2. Here, contrast represents the ratio of parallel transmittance and orthogonal transmittance (contrast = parallel transmittance at maximum absorption wavelength (Ky) / orthogonal transmission at maximum absorption wavelength (Kz)), and the larger this value, the more excellent the polarization performance of the polarizing plate is. Indicates. In addition, evaluation of polarization performance produced and compared the sample so that the parallel transmittance of the maximum absorption wavelength of a dye-type polarizing film might become the same. As shown in Table 2, the dye-based polarizing films of Examples F1 to F22 all had high contrast as compared with the dye-based polarizing films of Comparative Examples 1 and 2.

(Example P1: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (A-19) obtained in Example E3 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P2: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (A-20) obtained in Example E4 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P3: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (A-61) obtained in Example E8 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P4: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (A-92) obtained in Example E9 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P5: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (A-95) obtained in Example E10 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P6: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (A-100) obtained in Example E12 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P7: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (B-17) obtained in Example E13 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P8: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (B-29) obtained in Example E16 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P9: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (B-48) obtained in Example E17 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P10: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (C-16) obtained in Example E19 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P11: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (C-19) obtained in Example E20 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

(Example P12: manufacture of neutral gray polarizing plate)

45 degreeC aqueous solution which made the compound of Formula (C-46) obtained in Example E21 0.1%, C. direct red 81 0.2%, C. direct blue 274 0.05%, and 0.1% of forget-me-not. Except using this, it carried out similarly to Example F1, and manufactured the polarizing film. The single-plate average transmittance in 380-700 nm of the obtained polarizing film was 42%, and the average transmittance of the orthogonal cross section was 0.02%, and had high polarization degree.

The triacetyl cellulose film (TAC film: Fujifilm company make: brand name TD-80U) was laminated on both surfaces of this polarizing film through the adhesive agent of polyvinyl alcohol aqueous solution, the support body which formed the AR layer using the adhesive was affixed, and TAC A dye-based polarizing plate (neutral gray polarizing plate) in which a / polarizing film / TAC / AR support was laminated in this order was obtained.

The neutral gray polarizing plates obtained in Examples P1 to P12 showed no change in single-sheet average transmittance even after elapse of 400 hours under conditions of 80 ° C. and 90% RH, and showed long-term durability even at high temperature and high humidity. In addition, the neutral gray polarizing plates of Examples P1 to P12 did not change the single plate average transmittance even after 200 hours had elapsed in the xenon light test, and were excellent in light resistance against long-term exposure to light. From these results, it turned out that the neutral gray polarizing plates of Examples P1-P12 are all high performance dye type polarizing plates which have the outstanding polarization performance and have moisture resistance, heat resistance, and light resistance.

Claims (22)

Formula (1) below:

(In formula, A <^1> and A <^2> respectively independently have a naphthyl group which may have a substituent selected from the group which consists of a hydroxyl group, the C1-4 alkoxy group which has a sulfo group, and a sulfo group, or a substituent. Is a phenyl group,
R ₁ to R ₆ each independently represent a hydrogen atom, a C 1-4 alkyl group, a C 1-4 alkoxy group, a C 1-4 alkoxy group having a sulfo group, a carboxyl group, a hydroxyl group, a halogen group, or a C 1-4 alkyl substituted acylamino group to be)
Azo compound represented by it, or its salt. The method of claim 1,
One or both of A ¹ and A ² (in each case independently), a sulfo group, a carboxy group, a C 1-4 alkoxy group having a sulfo group, a C 1-4 alkyl group, a C 1-4 alkoxy group, a halogen group, a nitro group, C1-4 alkyl substituted amino groups, such as an amino group, N, N-dimethylamino group, N, N-diethylamino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, and acetylamino group, An azo compound or its salt which is a phenyl group which has one or more substituents chosen from the group which consists of C1-4 alkyl substituted acylamino groups, such as a propionamide group and a butylamide group. The method according to claim 1 or 2,
One or both of A ¹ and A ² (in each case, each independently) has at least one substituent selected from a sulfo group, a carboxyl group, and a C1-4 alkoxy group having a sulfo group, and a hydrogen atom, a sulfo group, or a carboxyl group. , A phenyl group further having a C1-4 alkoxy group having a sulfo group, a C1-4 alkyl group, a C1-4 alkoxy group, a halogen group, a nitro group, an amino group, a C1-4 alkyl substituted amino group, or a C1-4 alkyl substituted acylamino group Phosphorus, azo compounds or salts thereof. The method according to any one of claims 1 to 3,
One or both of A ¹ and A ² (in each case, each independently), the following formula (2):

(In formula, one of R <_7> and R <_8> is a C1-4 alkoxy group which has a sulfo group, a carboxyl group, or a sulfo group, and the other is a C1-4 alkoxy group, C1 which has a hydrogen atom, a sulfo group, a carboxy group, and a sulfo group. 4-4 alkyl group, C1-4 alkoxy group, halogen group, nitro group, amino group, C1-4 alkyl substituted amino group, or C1-4 alkyl substituted acylamino group)
An azo compound or its salt which is a phenyl group represented by these. The method of claim 4, wherein
An azo compound or its salt whose one of R <_7> and R <_8> is a sulfo group or a carboxyl group, and the other is a hydrogen atom, a sulfo group, a carboxy group, a methyl group, or a methoxy group. The method according to any one of claims 1 to 5,
At least one of A ¹ and A ² is the naphthyl group, an azo compound or a salt thereof. The method according to any one of claims 1 to 6,
An azo compound or its salt whose both A <^1> and A <^2> are the said phenyl groups. The method according to any one of claims 1 to 6,
One or both of A ¹ and A ² (in each case, each independently), and the following formula (3):

(In formula, R <_9> is a C1-4 alkoxy group or sulfo group which has a hydrogen atom, a hydroxyl group, a sulfo group, and n is an integer of 1-3.)
An azo compound or its salt which is a naphthyl group shown by these. The method of claim 8,
An azo compound or its salt whose R <_9> is a hydrogen atom and n is 2. The method according to any one of claims 1 to 9,
Formula (4) below:

(Wherein R ₁ to R ₆ are as defined in formula (1))
Represented by an azo compound or a salt thereof. The method according to any one of claims 1 to 5,
Formula (5) below:

(In formula, at least 1 of R <_10> -R <_13> is a sulfo group, Other than that, it is a C1-4 alkoxy group, methyl group, or methoxy group which has a hydrogen atom, a sulfo group, a carboxyl group, a sulfo group, and R <_1> -R <_6> is As defined in equation (1))
Represented by an azo compound or a salt thereof. The method according to any one of claims 1 to 11,
An azo compound or its salt whose R <_1> -R <_6> is a C1-4 alkoxy group which has a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a halogen group, or a sulfo group each independently. The method according to any one of claims 1 to 12,
An azo compound or its salt which R <_1> -R <_6> is respectively independently C1-4 alkoxy group which has a sulfo group, a hydrogen atom, a methyl group, an ethyl group, a halogen group, or a methoxy group. The method according to any one of claims 1 to 13,
An azo compound or its salt whose at least 1 of R <_1> -R <_6> is a C1-4 alkoxy group which has a sulfo group. The method of claim 14,
An azo compound or its salt whose C1-4 alkoxy group which has the said sulfo group is 3-sulfopropoxy group. The dye type polarizing film containing the polarizing film base material containing the azo compound in any one of Claims 1-15, or its salt. The dye-based polarizing film containing the azo compound in any one of Claims 1-15, or its salt, and the polarizing film base material containing one or more types of organic dyes other than these. The method according to claim 16 or 17,
The dye type polarizing film whose said polarizing film base material is a film which consists of polyvinyl alcohol resin or its derivative (s). The dye-based polarizing plate in which the transparent protective layer is bonded to the single side | surface or both surfaces of the dye-type polarizing film in any one of Claims 16-18. The polarizing plate for liquid crystal displays provided with the dye type polarizing film of any one of Claims 16-18, or the dye type polarizing plate of Claim 19. The neutral gray polarizing plate provided with the dye type polarizing film of any one of Claims 16-18, or the dye type polarizing plate of Claim 19. The liquid crystal display device provided with the dye-type polarizing plate of Claim 19, the polarizing plate for liquid crystal display of Claim 20, or the neutral gray polarizing plate of Claim 21.