WO2007145159A1 - Azo dye for anisotropic dye film - Google Patents

Abstract

Disclosed is an organic dye with excellent durability, which has strong dichroism in a short wavelength range (380-500 nm) and is useful for anisotropic dye films such as polarizing films. Specifically disclosed is an azo dye for anisotropic dye films, whose free acid form is represented by the following formula (1). In the formula (1), D1 represents an optionally substituted phenyl group or naphthyl group; R1-R4 independently represent a hydrogen atom, a sulfo group, a carboxy group, an optionally substituted alkyl group having 1-4 carbon atoms or an optionally substituted alkoxy group having 1-4 carbon atoms; n represents 0 or 1; and K1 represents a group represented by the formula (1-1) below or the like. (1-1) In the formula (1-1), ring A may have a substituent other than -OR5; and R5 represents a hydrogen atom, an optionally substituted alkyl group having 1-6 carbon atoms or an optionally substituted phenyl group.

Description

 Specification

 Azo dyes for anisotropic dye films

 Field of Invention

 [0001] The present invention is useful for light-emitting display elements such as light control elements, liquid crystal elements (LCD), and organic-electric-luminescence elements (OLE D), and polarizing plates included in input / output elements such as touch panels. The present invention relates to an azo dye for an anisotropic dye film.

 Background of the Invention

 [0002] In recent years, flat displays such as LCDs are widely used in television receivers, and are being replaced by conventional televisions using CRT. In addition, the color reproducibility of NTSC, which is the current television system, is determined based on the characteristics of the CRT phosphor, and there is a problem that only about half of the color of an existing object can be expressed. On the other hand, imaging devices such as digital cameras and camcorders have recently been able to express a wider range of colors (color reproduction) than the range defined by NTSC, and support extended color spaces that reproduce that information more accurately. A new display is desired.

 [0003] In this background, flat-type displays that replace CRTs, such as LCDs, are devices that, in principle, can express more saturated colors than CRTs, and are new movies that make use of the high functionality of flat-type displays. Standardization of extended color space has been promoted. As a result, according to the international standard IEC61966-2-4, “Extended-gamut YC color space for video application-xyYuC” has been developed.

 [0004] The xyYCC color space is a standard that can express almost all of the actual object colors, and it has become possible to express the material feeling of a colorful object as well as the stereoscopic effect.

 [0005] However, when the extended color space information is to be displayed on a conventional LCD, the characteristics of the various components used in the LCD are not sufficient, so that a display corresponding to the xyYCC color space can be constructed. Some improvements have been made.

 [0006] As an example,

 (1) Adoption of backlight with good color purity of RGB3 primary colors,

(2) Adoption of micro color filter with complementary colors added to RGB3 primary colors Etc.

 The typical means of (1) is the use of LEDs and the optimization of the emission wavelength of phosphors used in cold-cathode tubes, and (2) is the use of micro color filters with yellow and cyan added. (See Patent Documents 1 and 2).

[0007] As described above, the factors governing the color reproducibility of the LCD are members related to light emission, which are members having absorption in the visible light wavelength range. As for the polarizing film, it has not been fully studied.

 [0008] To support the xyYCC extended color space, it is necessary to improve the characteristics of the short-wavelength region and the long-wavelength region that hit both ends of the visible light, as estimated from the improvements of the backlight and micro color filter. It is.

 However, the conventional polarizing film has a problem that the contrast ratio at a specific wavelength or color is lowered because optical characteristics such as absorbance and dichroism in the visible light wavelength region are not constant. In particular, due to the low dichroism in the short wavelength region (380 nm to 500 nm), which is the complementary color of blue light, the color purity of blue light is lowered and color reproducibility cannot be obtained sufficiently.

 [0010] In addition to displays that support extended color spaces, in the case of liquid crystal projectors and in-vehicle liquid crystal panels, organic dyes that have dichroism that is less than iodine are used due to durability problems at high temperatures. Dye that absorbs at short wavelengths has a smaller π-conjugate spread than dyes that absorb at long wavelengths, so the sufficient aspect ratio required for dichroic dyes cannot be obtained. However, the development of dyes having high dichroism in the short wavelength region has been desired. In these applications, since durability at high temperatures is required, there is a problem that defects such as frame failure or frame unevenness due to shrinkage of the film accompanying temperature and humidity changes occur. The development of new dichroic dyes is also desired because the combination of polymer materials such as modified polybulal alcohols (polybulal alcohol derivatives) and dichroic substances that solve the problem has become important. Patent Document 1: Japanese Unexamined Patent Publication No. 2007-73290

Patent Document 2: Japanese Unexamined Patent Application Publication No. 2007-25285 Summary of the Invention

 An object of the present invention is to provide an organic dye for an anisotropic dye film having absorption in a short wavelength region (380 nm to 500 nm) that is useful for a polarizing film capable of expressing a wide range of colors. Another object of the present invention is to provide an organic dye for an anisotropic dye film having excellent durability.

 [0012] The azo dye for anisotropic dye film of the present invention is characterized in that the form of the free acid is represented by the following formula (1).

 [Chemical 1]

In the formula (1), D ¹ represents a phenyl group which may have a substituent or a naphthyl group which may have a substituent.

1 ^ to 1 ⁴ are each independently a hydrogen atom, a sulfo group, a carboxy group, the number alkyl group or C may have a substituent group having 1 to 4 carbon atoms which may have a substituent 1 Represents an alkoxy group of ~ 4.

 n represents 0 or 1.

K ¹ represents any one of the following formulas (1 1:!) To (1 1 3).

[0014] [Chemical 2]

(1-1) In formula (1-1), ring A may have a substituent other than —OR ⁵ . R ⁵ may have a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms or a substituent. Represents a good phenyl group.

 [0015] [Chemical 3]

(1-2) In formula (1-2), ring B may have a substituent other than _NR ⁶ R ⁷ . R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent or a substituent, or a vinyl group. Represents.

 [0016]

式（1— 3)中、 Q¹¹および Q¹は、それぞれ独立に、酸素原子または NH基を表す。 R⁹¹および R⁹²は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル 基または置換基を有していてもよいアミノ基を表す。 R⁹¹と R⁹²は、結合して環を形成し ていてもよい。

In formula (1-3), Q ¹¹ and Q ¹ each independently represents an oxygen atom or an NH group. R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amino group which may have a substituent. R ⁹¹ and R ⁹² may be bonded to form a ring.

 Detailed description

 According to the present invention, there is provided an organic dye that is useful for an anisotropic dye film such as a polarizing film and has high dichroism in the short wavelength region (380 nm to 5 OOnm) and excellent durability. .

 Hereinafter, embodiments of the azo dye for anisotropic dye film of the present invention will be described in detail.

 The description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not specified by these contents.

[0019] The anisotropic dye film referred to in the present invention refers to the electric current in any two directions selected from a total of three directions in the three-dimensional coordinate system in the thickness direction of the dye film and in any two orthogonal planes. It is a dye film having anisotropy in magnetic properties. The electromagnetic properties include optical properties such as absorption and bending, and electrical properties such as resistance and capacitance. Examples of the film having optical anisotropy such as absorption and refraction include a linear polarizing film, a circular polarizing film, a retardation film, and a conductive anisotropic film.

 [0020] The dye film referred to in the present invention refers to a layer containing a dye, and usually includes a layer containing a low molecular material and / or a polymer material, and is composed of, for example, only a dye. It may be a layer.

 The anisotropic dye film produced using the azo dye for anisotropic dye film of the present invention is used for a polarizing film which is preferably used for a functional film having absorption anisotropy as a main effect. It is more preferable.

In the present invention, “may have a substituent” means having 1 or 2 or more substituents.

[0022] [azo dye for anisotropic dye film]

 The azo dye for anisotropic dye film of the present invention is characterized in that the form of the free acid is represented by the following formula (1).

[0023] [Chemical 5]

式（1)中、 D¹は、置換基を有していてもよいフエニル基または置換基を有していて もよいナフチル基を表す。

In formula (1), D ¹ represents a phenyl group which may have a substituent or a naphthyl group which may have a substituent.

1 ^ to 1 ⁴ are each independently a hydrogen atom, a sulfo group, a carboxy group, the number alkyl group or C may have a substituent group having 1 to 4 carbon atoms which may have a substituent 1 Represents an alkoxy group of ~ 4.

 n represents 0 or 1.

K ¹ represents any one of the following formulas (1 1:!) To (1 1 3). [0025] [Chemical 6]

(ii) In formula (1-1), ring A may have a substituent other than —OR ⁵ . R ⁵ represents a hydrogen atom, a C 1-6 alkyl group which may have a substituent, or a phenyl group which may have a substituent.

 [Chemical 7]

式（1— 2)中、環 Bは、—NR⁶R⁷以外にも置換基を有していてもよレ、。 R⁶および R⁷ は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数 1〜6のアルキル 基または置換基を有してレ、てもよレ、フヱ二ル基を表す。

In formula (1-2), ring B may have a substituent other than —NR ⁶ R ⁷ . R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent or a substituent, or a vinyl group. Represents.

[0027] [Chemical 8]

式（1— 3)中、 Q¹¹および Q¹²は、それぞれ独立に、酸素原子または NH基を表す。 R⁹¹および R⁹²は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル 基または置換基を有していてもよいアミノ基を表す。 R⁹¹と R⁹²は、結合して環を形成し ていてもよい。 [0028] <^^⁴ >

In formula (1-3), Q ¹¹ and Q ¹² each independently represents an oxygen atom or an NH group. R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amino group which may have a substituent. R ⁹¹ and R ⁹² may be bonded to form a ring. [0028] <^^ ⁴ >

1 ^ to 1 ⁴ are each independently a hydrogen atom, a sulfo group, a carboxy group, the number alkyl group or C may have a substituent group having 1 to 4 carbon atoms which may have a substituent 1 Represents an alkoxy group of ~ 4.

 [0029] The alkyl group which may have a substituent is usually an alkyl group having 1 to 4, preferably 3 or less carbon atoms. Examples of the group that may be substituted on the alkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkyl group include a methyl group and an ethyl group.

 [0030] The alkoxy group which may have a substituent is usually an alkoxy group having 1 to 4 carbon atoms, preferably 3 or less carbon atoms. Examples of the group that may be substituted on the alkoxy group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, hydroxyethoxy group, 2,3-dihydroxypropoxy group and the like. An alkoxy group is mentioned.

[0031] <D ^X >

D ¹ represents a substituent having a substituent, or may be a phenyl group or a substituent, or may be a substituent or a naphthyl group.

[0032] Examples of the substituent that D ¹ may have include a sulfo group, a carboxy group, a hydroxyl group, a nitro group, an alkoxy group that may have a substituent, and an amino group that may have a substituent. Group, optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted rubamoyl group, optionally substituted sulfamoyl group And a substituent having a substituent, a phenyl group, a phenyl group, a substituent having a substituent, a fluorine group, an aryloxy group, and the like.

 [0033] The alkoxy group as a substituent usually has 1 or more carbon atoms, usually 6 or less, preferably 4 or less. Examples of the group which may be substituted on the alkoxy group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group and a carboxy group.

[0034] Specific examples of the alkoxy group include a substituent such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a hydroxyethoxy group, and a 2,3-dihydroxypropoxy group. Les, mayole and alkoxy groups, and particularly those having substituents are preferred.

The amino group as a substituent is usually represented by NH NHR ⁸¹ NR ⁸² R ⁸³ . R ⁸¹

 2

R ⁸³ each independently represents an alkyl group which may have a substituent, an optionally substituted group, a phenyl group or a substituted group, or an optionally substituted group. . The alkyl group usually has 1 or more carbon atoms, usually 12 or less, and preferably 10 or less. The isyl group is represented by-COR ⁸⁴ , and R ⁸⁴ is an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an alkenyl which may have a substituent. Represents a phenyl group which may have a group or a substituent. The alkyl group and the alkoxy group each have usually 1 or more carbon atoms, usually 6 or less, and preferably 4 or less. Each of the alkenyl groups has usually 1 or more carbon atoms, usually 12 or less, preferably 10 or less. Examples of the group that may be substituted on the alkyl group, the alkoxy group, the alkenyl group, and the phenyl group include an alkoxy group, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom. Alkyl group R ⁸¹ ~ ^3, as the group but it may also be substituted on phenyl group or Ashinore group which may have a substituent phenyl group, an alkoxy group, a hydroxyl group, a sulfo group, a carboxy group and a halogen atom Etc. Examples of the group that may be substituted on the phenyl group include a C 14 alkyl group, a C 14 alkoxy group, a sulfo group, a carboxy group, and a hydroxyl group.

 [0036] Specific examples of the amino group include an amino group, a methylamino group, an ethylamino group, a 2-sulfochinoleamino group, a 4-sulfophenylamino group, a 4-carboxybenzoylamino group, and a fumarylamino group. It is done.

 [0037] The alkyl group as a substituent has usually 1 or more, usually 6 or less, preferably 4 or less carbon atoms. Examples of the group that may be substituted on the alkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group.

 [0038] Specific examples of the alkyl group include a methyl group, an ethyl group, and the like. Particularly, the alkyl group may have a substituent, and may be a lower alkyl group.

[0039] The alkenyl group as a substituent usually has 1 or more, usually 12 or less, preferably 10 or less carbon atoms. Examples of the group which may be substituted on the alkenyl group include an alkyl group and phenyl. Group and carboxy group.

 [0040] Specific examples of the alkenyl group include a trans 2 carboxyethenyl group, a trans 2 mono (2-sulfophenyl) ethenyl group, and the like.

[0041] The powerful rubamoyl group as a substituent has usually 1 or more, usually 6 or less, preferably 4 or less. Examples of the group which may be substituted on the carbamoyl group include an optionally substituted alkyl group having 1 to 4 carbon atoms.

[0042] Specific examples of the force rubamoyl group may include a force rubamoyl group, N

—Methylcarbamoyl group can be mentioned.

[0043] The sulfamoyl group as a substituent has usually 1 or more, usually 6 or less, preferably

4 or less. Examples of the group which may be substituted on the sulfamoyl group include an optionally substituted alkyl group having 1 to 4 carbon atoms.

 (Specific examples of the sulfamoyl group having a substituent include sulfamoyl group and N-methylsulfamoyl group.

[0044] The phenyl group as a substituent has usually 6 or more carbon atoms, usually 10 or less, preferably 8 or less. Examples of the group that may be substituted on the phenyl group include an alkoxy group, a hydroxyl group, a sulfo group, and a carboxy group. Specific examples thereof include a phenyl group which may have a substituent such as a phenyl group, a 3-sulphophenyl group, and a 4-sulfophenyl group.

 [0045] The aryl group constituting the aryloxy group as a substituent is preferably a phenyl group or a naphthyl group. The substituent that the aryl group may have is an alkyl group, an alkoxy group, a carboxy group. Group, sulfo group, hydroxyl group and the like.

 Specific examples of the aryloxy group which may have a substituent include a phenoxy group, a 2-naphthoxy group, a ρ-tolyloxy group, a ρ-methoxyphenoxy group, an o_carboxyphenoxy group, and the like.

[0046] D ¹ is preferably a phenyl group or a naphthyl group having one or more water-soluble groups selected from the group consisting of a sulfo group and a carboxy group as a substituent. In particular, D ¹ is a phenyl group having 1 or 2 water-soluble groups selected from the group consisting of a sulfo group and a carboxy group, or a naphthyl group having! To 3 water-soluble groups as a substituent. Preferably there is.

[0047] When D ¹ is a phenyl group, the water-soluble group is preferably bonded to the para-position of the benzene ring to which the azo group is bonded.

Further, when D ¹ is a naphthyl group, it is preferable that an azo group is bonded to the 2-position of the naphthalene ring. In this case, the water-soluble group is preferably bonded to the 6th and 8th positions of the naphthalene ring.

D ¹ may have a substituent other than the water-soluble group, but preferably has only the water-soluble group as a substituent.

[0048] <K ^X >

Κ ¹ represents any of the following formulas (1 1:!) To (1_3).

[0049] [Chemical 9]

In the formula (1-1), the ring may have a substituent other than —OR ⁵ . IT represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.

[0050] Examples of the alkyl group which may have a substituent group R ^5, usually, one or more carbon atoms, 6 or less, preferably 4 or less, more preferably 3 or less alkyl groups. Examples of the group that may be substituted for the alkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkyl group include a methyl group and an ethyl group.

[0051] R ⁵ may have a substituent, may be substituted, or may be substituted with a phenyl group. The group may be an alkyl group which may have a substituent (the substituent Examples of the group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfo group, and a carboxy group.), An alkoxy group, a carboxy group, a sulfo group, and a hydroxyl group. Specific examples of the phenyl group Examples include phenyl group, p-trinole group, p-methoxyphenyl group, o carboxyphenyl group, and the like.

The substituent that ring A may have other than —OR ⁵ includes a sulfo group, a carboxy group, a hydroxyl group, an alkyl group that may have a substituent, and a substituent. Examples thereof may include an alkoxy group that may be substituted and an amino group that may have a substituent. Ring A may have one of these substituents, or may have two or more.

 [0053] The alkyl group which may have a substituent is usually an alkyl group having 1 to 6, preferably 3 or less carbon atoms. Examples of the group that may be substituted on the alkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkyl group include a methyl group, an ethyl group, and the like. Particularly, the alkyl group preferably has a substituent, and may be a lower alkyl group.

 [0054] The alkoxy group which may have a substituent is usually an alkoxy group having 1 to 4 carbon atoms, preferably 3 or less carbon atoms. Examples of the group that may be substituted on the alkoxy group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n butoxy group, hydroxyethoxy group, 2,3 dihydroxypropoxy group and the like. Particularly preferred are those having a substituent, and a lower alkoxy group.

[0055] The amino group optionally having substituent (s) is usually NH NHR ²¹ -NR¾

 2

²³ , —NHCOR ²⁴ , and each R ²¹ R ²⁴ independently represents an alkyl group which may have a substituent or a phenyl group which may have a substituent. The alkyl group usually has 1 or more carbon atoms, usually 4 or less, and preferably 2 or less. Examples of the group that may be substituted on the alkyl group and the phenyl group include an alkoxy group, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom. Specific examples of the amino group include a methylamino group, an ethylamino group, a propylamino group, a dimethylamino group, a phenylamino group, an acetylamino group, and a benzoylamino group.

[0056] [Chemical 10]

In formula (1-2), ring B may have a substituent other than _NR ⁶ R ⁷ . R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent or a substituent, or a vinyl group. Represents.

[0057] Specific examples of the case where R ⁶ and R ⁷ have a substituent and are an alkyl group are the same as those of the alkyl group of R ⁵ described above.

Further, specific examples in the case where R ⁶ and R ⁷ are optionally substituted phenyl groups are the same as the above R ⁵ phenyl group.

The substituent that ring B may have other than —NR ⁷ is the same as that exemplified as the substituent of ring A above.

 [Chemical 11]

式（1— 3)中、 Q¹¹および Q¹²は、それぞれ独立に、酸素原子または NH基を表す。 R⁹¹および R⁹²は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル 基または置換基を有していてもよいアミノ基を表す。 R⁹¹と R⁹²は、結合して環を形成し ていてもよい。

In formula (1-3), Q ¹¹ and Q ¹² each independently represents an oxygen atom or an NH group. R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amino group which may have a substituent. R ⁹¹ and R ⁹² may be bonded to form a ring.

[0059] The alkyl group which may have a substituent of R ⁹¹ and R ⁹² has usually 1 or more carbon atoms, usually 6 or less, preferably 4 or less. Examples of the group that may be substituted on the alkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkyl group include a methyl group and an ethyl group. It has a lower alkyl group.

[0060] The amino group optionally having a substituent of R ⁹¹ and R ⁹² is usually —NH, —NHR ^2U ,

 2

— Represented by NR ^{21 213} . R ^{2U to} R ²¹³ are each independently an alkyl group which may have a substituent, a substituent having a substituent, a substituent, a phenyl group or a substituent having a substituent. Represents an acyl group. The alkyl group usually has 1 or more carbon atoms, usually 12 or less, and preferably 10 or less. The acyl group is represented by —COR ²¹⁴ , and R ²¹⁴ may have an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or may have a substituent. It represents an alkenyl group or a phenyl group which may have a substituent. The alkyl group and the alkoxy group each have usually 1 or more carbon atoms, usually 6 or less, preferably 4 or less. Each of the alkenyl groups has usually 1 or more, usually 12 or less, preferably 10 or less. Examples of the group that may be substituted on the alkyl group, the alkoxy group, the alkenyl group, and the phenyl group include an alkoxy group, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom.

[0061] As the alkyl group, group which may be substituted on phenyl group or Ashinore group R to R ^213, an optionally substituted phenyl group, an alkyl group, an alkoxy group, Ashiruamino group, a hydroxyl group, Examples include a sulfo group, a carboxy group, and a halogen atom. Examples of the group that may be substituted on the phenyl group include a sulfo group, a carboxy group, and a hydroxyl group.

[0062] When R ⁹¹ and R ⁹² are combined to form a ring, a group having a carbonyl group, a thiocarbonyl group, or the like can be used as a substituent for the amino group.

 [0063] The group represented by the formula (13) is preferably a group represented by the following formula (14) or the following formula (15).

[0064] [Chemical 12]

In formula (1-4), R ¹¹ and each independently represent a hydrogen atom, a halogen atom, a sulfo group, a carboxy group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or a substituent. It has an alkoxy group having 1 to 4 carbon atoms or a substituent, and it may have an acyl group having 1 to 7 carbon atoms.

[0065] Specific examples of the case where R ¹¹ and R ¹² have a substituent and are an alkyl group are the same as the alkyl group of R ⁵ described above.

[0066] R ¹¹ and R ¹² force In the case of an optionally substituted alkoxy group, the optionally substituted alkoxy group has 1 to 4 carbon atoms, preferably 3 or less alkoxy groups. Examples of the group which may be substituted on the alkoxy group include an alkoxy group

, Hydroxyl group, halogen atom, sulfo group and carboxy group. Specific examples of the alkoxy group include an alkoxy group which may have a substituent such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a hydroxyethoxy group, or a 2,3-dihydroxypropoxy group. Is mentioned.

[0067] The acyloamino group which may have a substituent is usually represented by one NHCOR ⁹⁹ , and R ⁹⁹ has a substituent, may be an alkyl group or a substituent. And represents a phenyl group. The alkyl group is an alkyl group having usually 1 or more, usually 4 or less, preferably 2 or less carbon atoms. Examples of the group that may be substituted on the alkyl group and the phenyl group include an alkoxy group, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom. Specific examples of the acylamino group include an acetylamino group and a benzoylamino group.

[0068] [Chemical 13]

In formula (1-5), R ″ and R ¹⁴ each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. X ¹ represents O or NH. Y ¹ represents 〇 or S.

[0069] Specific examples in the case where R ¹³ and R ¹⁴ are an optionally substituted alkyl group include

The same as the alkyl group for R ⁵ above.

[0070] The group represented by the formula (13) preferably has 3 to 12 carbon atoms, and specific examples thereof include the following.

[0071] [Chemical 14]

[0072] <n>

 n represents 0 or 1.

[0073] <Molecular weight>

 The molecular weight of the azo dye for the anisotropic dye film represented by the formula (1) (hereinafter referred to as “the dye of the present invention”) is 1500 or less, preferably 1500 or less in the form of a free acid. Is more preferable.

[0074] <Water-soluble>

 The dye of the present invention is usually a water-soluble dye.

[0075] <Salt type> The dye of the present invention may be used as it is in the free acid form (free acid form), or a part of the acid group may have a salt form. Further, a salt-type dye and a free acid-type dye may be mixed. Moreover, when it is obtained in a salt form at the time of production, it may be used as it is, or it may be converted into a desired salt form. As a salt type exchange method, a known method can be arbitrarily used, and examples thereof include the following methods.

 [0076] 1) A strong acid such as hydrochloric acid is added to an aqueous solution of a dye obtained in a salt form, and the dye is acidified in the form of a free acid, and then an alkali solution having a desired counter ion (for example, sodium hydroxide aqueous solution). Solution, neutralizing the acidic group of the dye with a lithium hydroxide aqueous solution), and exchanging the salt.

 2) A method of performing salt exchange in the form of a salting-out cake by adding a large excess of a neutral salt (for example, sodium chloride or lithium chloride) having a desired counter ion to an aqueous solution of a dye obtained in a salt form.

 3) An aqueous solution of the dye obtained in salt form is treated with a strongly acidic cation exchange resin, the dye is acidified in the form of a free acid, and then an alkali solution having a desired counter ion (for example, hydroxide) Method of neutralizing dye acidic groups and salt exchange with aqueous solution of sodium and lithium hydroxide)

4) An aqueous solution of a dye obtained in a salt form is allowed to act on a strongly acidic cation exchange resin that has been previously treated with an alkaline solution having a desired counter ion (for example, an aqueous solution of sodium hydroxide or an aqueous solution of lithium hydroxide). How to do.

 [0077] Whether the acidic group of the dye of the present invention takes the free acid form or the salt form depends on the pKa of the dye and the pH of the dye solution. Therefore, the acidic group of the dye of the present invention may be a free acid type, any salt type, and when there are two or more acidic groups, a mixture of a free acid type and a salt type or a mixture of two or more salt types, etc. Can take a variety of forms. In particular, the acidic group of the azo dye in the anisotropic dye film is a preferred pH of the composition for anisotropic dye film described later or a dissociable salt of the substrate containing the dye for anisotropic dye film. Under the influence of the treatment with the solution containing it, it may have a salt form different from that used in the step of forming the anisotropic dye film.

 [0078] Examples of the above salt types include salts of alkali metals such as Na, Li, K, etc., substituted with an alkyl group or a hydroxyalkyl group, and may be a salt of ammonium, or an organic amine. Salt.

[0079] Examples of organic amines include lower alkylamines having from 6 to 6 carbon atoms and hydroxy-substituted charcoal. Prime numbers: lower alkylamines having! To 6 and carboxy-substituted lower alkylamines having 1 to 6 carbon atoms.

 In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed. Further, a plurality of types may be mixed in one molecule of the compound, or a plurality of types may be mixed in the composition.

 [0080] The preferred type of the acidic group of the dye of the present invention varies depending on the production process of the dye, the content of the composition for anisotropic dye film described later, and the preferred pH, but high solubility in water is required. In some cases (for example, when a high dye concentration is required in the composition for an anisotropic dye film in order to enhance the ability of dye transfer to a substrate), an organic compound substituted with a lithium salt, triethylamine salt, or a water-soluble group It is preferable to have one or more amine salts or these salts. On the other hand, when low solubility in water is required (for example, when the dye is to be precipitated from the dye solution in the dye production process), the free acid type, sodium salt, potassium salt, calcium salt, etc. It is preferred to have at least one alkaline earth metal salt or one of these salts.

 [0081] <Specific example>

 Specific examples of the dye of the present invention are shown below, but the present invention is not limited thereto. In addition, the following specific examples are described in the form of a free acid.

[0082] [Chemical 15]

[0084] [Chemical 17]

[8ΐ ^>] [9800]

80.T90 / .OOZdf / X3d OS 6STSM / .00Z OAV [9800]

(ΖΖ ~ Ζ)

80.T90 / .00Zdf / X3d 6STSM / .00Z OAV

[0087] Gu Production Method>

 The dye of the present invention can be produced according to a method known per se. For example, the dye represented by the above No. (2-1) can be produced by the following method. That is, 4-aminobenzene-4'-sodium sulfonate is prepared by a conventional method [eg, Yutaka Hosoda, Shin Dye Chemistry ”(December 21, 1978, published by Gihodo), page 396, page 409] is diazotized and condensed with 2-hydroxybenzoic acid (salicylic acid) to obtain the target dye No. (2— 1) is obtained.

[0088] Composition for anisotropic dye film

In producing the anisotropic dye film, the composition for anisotropic dye film can be used. The

 The composition for anisotropic dye films contains the dye of the present invention, and usually further contains a solvent. In this composition or in the anisotropic dye film described in detail below, the dye of the present invention can be used alone, but the dye of the present invention is used in combination with other dichroic substances such as iodine. You can also Furthermore, it can be used by mixing with other dyes such as an ultraviolet absorbing dye and a near infrared absorbing dye to such an extent that the orientation is not lowered. As a result, it is possible to improve the durability of the anisotropic dye film, correct the hue, improve the polarization performance, and manufacture anisotropic dye films having various hues.

 [0089] Water, water-miscible organic solvents, or mixtures thereof are suitable as the solvent used in the anisotropic dye film composition. Specific examples of organic solvents include methanol alcohols such as methyl alcohol, etheno-leanolol and isopropyleno-le-no-conole, glycols such as ethylene glycol and diethylene glycol, and methyl solvates such as methyl solvate and cetyl solvate. Aprotic solvents such as N-methylpyrrolidone and N, N-dimethylformamide, or a mixture of two or more of them.

 [0090] The concentration in which the dye is dissolved in these solvents depends on the solubility of the dye and the formation concentration of the associated state, but is preferably 0.001% by weight or more, more preferably 0.01% by weight. Above, preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less.

 [0091] In addition, an additive such as a surfactant can be added to the anisotropic dye film composition as necessary to improve the solubility of the dye. As the surfactant, any of anionic, cationic and nonionic surfactants can be used. The concentration of addition is usually preferably 0.01% by weight or more and 10% by weight or less.

Furthermore, the anisotropic dye film composition according to the present invention can use additives as necessary in order to improve the dyeing property to the substrate. Specifically, Asahara Teruzo “New Dye Processing Course 7th Dyeing II”, Kyoritsu Shuppan Co., Ltd., published on June 15, 1972, pp. 233-251 and co-authored by Yuya Yamashita and Yoshiro Nemoto “Polymer Activator” Seibundo Shinkosha Co., Ltd., published on September 5, 1963, pages 94 to 173, etc. Surfactant, alcohol, glyco And inorganic salts such as urea, urea, sodium chloride, and sodium nitrate. Its concentration is usually 0.

It is preferably 01% by weight or more and 10% by weight or less.

[0093] [Anisotropic dye film]

 An anisotropic dye film can be produced using the dye of the present invention.

 In addition to the dye of the present invention, the anisotropic dye film may contain other dyes as necessary, for example,

Further, it may contain an additive such as a known blue dichroic dye, iodine or the like, or a surfactant as described above. Of course, you may contain combining the pigment | dye represented by the pigment | dye of this invention.

 [0094] Examples of the method for producing the anisotropic dye film include the following methods (a) to (c).

 (a) A method of dyeing a stretched polymer base material such as polybutyl alcohol with a dye-containing solution (an anisotropic dye film composition) or the like

 (b) A method in which a polymer base material such as polyvinyl alcohol is dyed with a dye-containing solution (an anisotropic dye film composition) or the like and then stretched.

 (c) A method in which a polymer base material such as polybulualcohol is dissolved in a solution containing a dye (an anisotropic dye film composition) or the like and formed into a film and then stretched.

 [0095] When forming an anisotropic dye film using the dye of the present invention, for example, in any of the methods (a) to (c), the azo dye is dissolved in an appropriate solvent. . Examples of the solvent include a solvent contained in the anisotropic dye film composition.

 [0096] The base material that is dyed with the dye solution in the methods (a) and (b) and the base material that is stretched together with the dye in the method (c) include polyvinyl alcohol resins, poly Examples include vinyl acetate resin, ethylene / vinyl acetate (EVA) resin, nylon resin, and polyester resin. Among them, a polymer material having a high affinity with a pigment such as polybulal alcohol is preferable.

[0097] As the type of polybulal alcohol, those having a high molecular weight and a high degree of chain are generally preferred from the viewpoint of optical properties such as polarization degree and dichroism, but defects due to shrinkage due to temperature and humidity are suppressed. In addition, for the purpose of achieving compatibility between optical properties and environmental resistance, polybulal alcohol derivatives with appropriate adjustment of the type of dichroic substances and the degree of saponification and modification of polybulal alcohol (ratio of hydrophobic copolymer components) Can be selected. [0098] As a specific method for controlling the interaction between the polymer material and the dye, the proton donating properties of each polymer material and the dye are 10 H, -NH, -NHR, -NHCO-, — NHCONH

 2

 For protons, etc., one of proton acceptability '= Ν—, —OH, — NH, -NRR', —OR,-

2

 It can be made effective by combining aromatic rings such as CN, _C 3 C- and phenyl groups or naphthyl groups as functional groups (R and are optional substituents). Furthermore, by adjusting the density of the functional group, an effect can be obtained in improving the dichroic dyeing property.

The dyeing, film formation and stretching in the methods (a) to (c) can be performed by the following general methods.

 [0100] In the dye bath containing the above-mentioned composition for anisotropic dye film and, if necessary, an organic salt such as sodium chloride and bow glass, and a dyeing assistant such as a surfactant, usually 35 ° C or higher The polymer film is immersed and dyed usually at 80 ° C or less and usually for 10 minutes or less, then treated with boric acid as necessary and dried. Alternatively, the high molecular weight polymer is dissolved in water and / or a hydrophilic organic solvent such as alcohol, daricerine, dimethylformamide, etc., and the anisotropic dye film composition according to the present invention is added to perform stock solution dyeing, The dyeing stock solution is formed into a film by casting, solution coating, extrusion method, and the like. The concentration of the polymer to be dissolved in the solvent varies depending on the kind of the polymer, but is usually 5% by weight or more, preferably about 10% by weight or more, usually 30% by weight or less, preferably 20%. Less than about wt%. The concentration of the dye dissolved in the solvent is usually 0.1% by weight or more, preferably about 0.8% by weight or more, and usually 5% by weight or less, preferably 2.5% with respect to the polymer. Weight% or less.

[0101] The unstretched film obtained by dyeing and forming a film as described above is stretched in a uniaxial direction by an appropriate method. By stretching, the dye molecules are oriented and dichroism develops. Examples of the uniaxial stretching method include a method of performing tensile stretching by a wet method, a method of performing tensile stretching by a dry method, a method of performing inter-roll compression stretching by a dry method, and the like. May be. The stretching ratio is 2 times or more and 9 times or less. However, when polybutyl alcohol and its derivatives are used as the polymer, the range is preferably 3 times or more and 6 times or less. [0102] After the stretching and orientation treatment, hydrofluoric acid treatment is carried out for the purpose of improving the durability and the degree of polarization of the stretched film. Boric acid treatment improves the light transmittance and degree of polarization of the anisotropic dye film. The conditions for the boric acid treatment vary depending on the type of the hydrophilic polymer used and the dye, but generally the boric acid concentration is usually 1% by weight or more, preferably about 5% by weight or more, usually 15%. It is about 10% by weight or less, preferably about 10% by weight or less. The treatment temperature is usually 30 ° C or higher, preferably 50 ° C or higher, and usually within the range of 80 ° C or lower. Boric acid concentration force Force less than 1% by weight \ If the treatment temperature is less than 30 ° C, the treatment effect will be small. Also, the force with boric acid concentration exceeding 15% by weight, and the treatment temperature should be 80 ° C or more If it exceeds, the anisotropic dye film becomes brittle, which is not preferable.

 [0103] The film thickness of the anisotropic dye film obtained by the methods (a) to (c) is usually 50 μm or more, particularly 80 μm.

 z m or more, 200 z m or less, force S is preferable, and 100 μm or less is particularly preferable.

 [0104] An anisotropic dye film containing the dye of the present invention utilizes a light absorption anisotropy and functions as a polarizing film for obtaining linearly polarized light, circularly polarized light, elliptically polarized light, etc. By selecting a composition containing a material and color, it can be functionalized as various anisotropic films such as refractive index anisotropy and conduction anisotropy, and polarized light applicable to various types and various applications. It can be used as an element.

 [0105] When the anisotropic dye film is used as a polarizing element, the anisotropic dye film itself prepared by the method represented by the above (a) to (c) may be used. A layer having various functions such as a protective layer, an adhesive layer, an antireflection layer, and a retardation layer may be laminated on the film and used as a laminate.

 [0106] When an anisotropic dye film containing the dye of the present invention is formed on a substrate and used as a polarizing element, the formed anisotropic dye film itself may be used. In addition to protective layer, adhesive layer or antireflection layer, alignment film, function as retardation film, function as brightness enhancement film, function as reflection film, function as transflective film, function as diffusion film, etc. A layer having various functions such as a layer having an optical function may be stacked by a wet film forming method or the like to be used as a stacked body.

[0107] These layers having an optical function can be formed, for example, by the following method. [0108] The layer having a function as a retardation film is subjected to, for example, a stretching process described in Japanese Patent No. 2841377, Japanese Patent No. 3094113, or a process described in Japanese Patent No. 3168850. Can be formed.

[0109] Further, the layer having a function as a brightness enhancement film may be formed by forming micropores by a method described in, for example, JP-A-2002-169025 or JP-A-2003-29030, or It can be formed by overlapping two or more cholesteric liquid crystal layers with different selective reflection center wavelengths.

[0110] The layer having a function as a reflective film or a transflective film can be formed using a metal thin film obtained by vapor deposition or sputtering.

[0111] The layer having a function as a diffusion film can be formed by coating the protective layer with a resin solution containing fine particles.

[0112] Further, the layer having a function as a retardation film or an optical compensation film can be formed by applying and aligning a liquid crystalline compound such as a discotic liquid crystalline compound or a nematic liquid crystalline compound. it can.

[0113] An anisotropic dye film using the dye of the present invention can express a wide range of colors, and can obtain a highly heat-resistant polarizing element, so that it is not limited to a liquid crystal display or an organic EL display. It can be suitably used for applications that require high heat resistance such as liquid crystal projectors and in-vehicle display panels.

 Example

 [0114] Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as it does not exceed the gist thereof.

In the following examples, the dichroic ratio was calculated by the following equation after measuring the transmittance of the anisotropic dye film with a spectrophotometer in which a prism polarizer was arranged in the incident optical system.

 Dichroic ratio (D) = Az / Ay

 Az = -log (Tz)

 Ay = — log (Ty)

 Tz: Transmittance for polarized light in the direction of the absorption axis of the dye film

Ty: Transmittance for polarized light in the direction of the polarization axis of the dye film [0116] Example 1

 In 100 parts by weight of distilled water, 0.05 part by weight of a dye salt of dye No. (2-1) having the following structural formula and 0.02 part by weight of anhydrous sodium sulfate were added and stirred and dissolved to obtain a dyeing solution. After immersing and dyeing polybulal alcohol film (〇PL Finolem) manufactured by Japan Synthetic Chemical Industry Co., Ltd. in a dyeing solution at 50 ° C for the time shown in Table 1, the excess dye is washed in a 50 ° C water bath. The film was stretched 6 times in a 4% by weight boric acid aqueous solution at 50 ° C. After stretching, excess boric acid was washed in a water bath at room temperature and dried by blowing to obtain an anisotropic dye film. The maximum absorption wavelength of this anisotropic dye film, the single transmittance at that wavelength, and the dichroic ratio are shown in Table 1. It was found that the film has high dichroism.

[0117] [Chemical 20]

[0118] Example 2

 Except that the sodium salt of the dye of the dye No. (2-1) above was changed to the sodium salt of the dye No. (2-9) of the following structural formula and the dyeing times shown in Table 1 were used. An anisotropic dye film was obtained in the same manner as in Example 1. The maximum absorption wavelength of this anisotropic dye film, the single transmittance at that wavelength, and the dichroic ratio are shown in Table 1. It was found that the anisotropic dye film has high dichroism.

[0119] [Chemical 21]

[0120] Example 3

Example 1 is the same as Example 1 except that the sodium salt of the dye No. (2_1) is changed to the sodium salt of the dye No. (2_8) having the following structural formula and the dyeing times shown in Table 1 are used. Same An anisotropic dye film was obtained using the above method. Table 1 shows the maximum absorption wavelength of this anisotropic dye film, the unit transmittance at that wavelength, and the dichroic ratio, but it has high dichroism.

[0121] [Chemical 22]

[0122] Example 4

 Except that the sodium salt of the dye of dye No. (2-1) was changed to the sodium salt of the dye of dye No. (2-5) having the following structural formula and the dyeing times shown in Table 1 were used. An anisotropic dye film was obtained in the same manner as in Example 1. Table 1 shows the maximum absorption wavelength of this anisotropic dye film, the unit transmittance at that wavelength, and the dichroic ratio, but it has high dichroism.

[0123] [Chemical 23]

(2-5)

[0124] Example 5

 Except that the sodium salt of the dye No. (2_1) is changed to the sodium salt of the dye No. (2-17) having the following structural formula and the dyeing times shown in Table 1 are used, the Examples An anisotropic dye film was obtained using the same method as in 1. The maximum absorption wavelength of this anisotropic dye film, the unit transmittance at that wavelength, and the dichroic ratio are shown in Table 1. It was found that the anisotropic dye film has high dichroism.

[0125] [Chemical 24]

[0126] Comparative Example 1

 Except that the sodium salt of the dye No. (2-1) was changed to the sodium salt of the dye No. (i-1) of the following structural formula and the dyeing times shown in Table 1 were used. An anisotropic dye film was obtained in the same manner as in Example 1. It was found that the force S and dichroism described in Table 1 are insufficient for the maximum absorption wavelength of this anisotropic dye film, the single transmittance at that wavelength, and the dichroic ratio.

[0127] [Chemical 25]

[0128] [Table 1]

[0129] This application is filed with a Japanese patent application filed on June 15, 2006 (Japanese Patent Application 2006-166285) and a Japanese patent application filed on August 2, 2006 (Japanese Patent Application). 2006 • 211121), which is incorporated by reference in its entirety.

Claims

The scope of the claims  The free acid form is represented by the following formula (1):

In formula (1), D ¹ represents a phenyl group which may have a substituent or a naphthyl group which may have a substituent. 1 ^ to 1 ⁴ are each independently a hydrogen atom, a sulfo group, a carboxy group, the number alkyl group or C may have a substituent group having 1 to 4 carbon atoms which may have a substituent 1 Represents an alkoxy group of ~ 4.  n represents 0 or 1. K ¹ represents any one of the following formulas (1 1:!) To (1 1 3). [Chemical 27]

(1-1) In formula (1-1), ring A may have a substituent other than —OR ⁵ . R ⁵ represents a hydrogen atom, a C 1-6 alkyl group which may have a substituent, or a phenyl group which may have a substituent. [Chemical 28]

In formula (1-2), ring B may have a substituent other than _NR ⁶ R ⁷ . R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent or a substituent, or a vinyl group. Represents.  [Chemical 29]

In formula (1-3), Q ¹¹ and Q ¹² each independently represents an oxygen atom or an NH group. R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amino group which may have a substituent. R ⁹¹ and R ⁹² may be bonded to form a ring. [2] D ¹ has 1 or more and a water-soluble group selected from the group consisting of sulfo and carboxy groups and substituents, characterized in that it is a phenyl group or a naphthyl group, No placing serial to claim 1 Azo dye for anisotropic dye film. [3] D ¹ is phenyl group having 1 or 2 said water-soluble group as a substituent, or characterized in that it is a naphthyl group having one to three water-soluble group as a substituent, claim 2. An azo dye for anisotropic dye film according to 2. 4. The anisotropic dye film according to claim 3, wherein D ¹ is a phenyl group in which the water-soluble group is bonded to the para-position of the benzene ring to which the azo group is bonded. For azo dyes. [5] D ¹ has an azo group bonded to the 2-position of the naphthalene ring, and the water-soluble group is bonded to the 6-position of the naphthalene ring. The anisotropic color according to claim 3, wherein the anisotropic color is a naphthyl group bonded to the 8-position. Azo dye for base film. [6] D ¹ is the a water-soluble group only substituents, and wherein the phenyl group or a naphthyl group der Rukoto of claim 3 for an anisotropic dye film § zone dyes. [7] ¹ to! ^ Are each independently a hydrogen atom, a sulfo group, a carboxy group, a methylol group, an ethyl group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a hydroxyethoxy group, 2. The azo dye for an anisotropic dye film according to claim 1, wherein the azo dye is a 2,3-dihydroxypropoxy group.  [8] The basic force S represented by the formula (11-3), the group represented by the following formula (11-4), or the following formula (11-5), The azo dye for anisotropic dye film | membrane of description.  [Chemical 30]

(1-4) In the formula (1-4), R ¹¹ and each independently represent a hydrogen atom, a halogen atom, a sulfo group, a carboxy group, or a C 1-4 alkyl which may have a substituent. It represents a group having a substituent, a substituent or a substituent, and an alkoxy group having 1 to 4 carbon atoms or a substituent having a substituent, or a substituent having a substituent, and a acyl group having 1 to 7 carbon atoms.  [Chemical 31]

(1-5) In formula (15), R ″ and R 1 each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. X ¹ represents O or NH. Y ¹ represents ○ or S. [9] K ^1, characterized in that a number 3 to 12 group atoms, according to claim 1 for an anisotropic dye film § zone dyes. [10] K ^1, characterized in that any one of groups represented by the following structural formula, the mounting serial to claim 1 for an anisotropic dye film § zone dyes.  [Chemical 32]