TW200815533A - Azo pigment for anisotropic pigment film - Google Patents

Abstract

The present invention relates to an organic pigment, which is suitable for use in anisotropic pigment films such as polarizing films and has high dichroism in the short wavelength region (380 nm to 500 nm) and excellent durability, and in particular, an azo pigment for anisotropic pigment film, of which the free acid form can be represented by the following formula (1) or (2).

Description

200815533 IX. Description of the Invention: [Technical Field] The present invention relates to a light-emitting display element such as a dimming element or a liquid crystal element (LCD), an organic electroluminescence element (0LED), or an input/output element such as a touch panel. The polarizing plate or the like provided is a useful azo dye for an anisotropic pigment film. [Prior Art] In recent years, flat-panel displays such as LCDs have been widely used in televisions, and _ is replacing the conventional televisions using CRTs. Further, the color reproducibility of the current television system, NTSC, depends on the phosphor characteristics of the CRT, and there is a problem that only about half of the color of the object is apparent. On the other hand, in recent years, an image pickup device such as a digital camera or a video camera has been able to perform color display (color reproduction) over a wider range defined by Ntsc, and thus the operator desires to have an expanded color space corresponding to more accurate reproduction of its information. The display.

In this context, LCDs and other flat-type displays that replace CRTs are the devices that are more colorful than CRTs in the original Luli. The industry has been promoting the new functions of high-performance features of flat-screening people. Use standardization of the expanded color space. As a result, "Extended-gamut YCC color space for video application-xy YCC" is issued as an international standard IEC61966_2-4. The xy YCC color space is a standard that can express the color of almost all real objects. This can also express the material sense or three-dimensionality of a brightly colored object. However, when the information about the expanded color space is to be expressed by the conventional LCD, the characteristics of the various components used in the LCD are not sufficient, so the 312XP/invention specification (supplement)/96-11/96119266 6 200815533 is constructed. The display corresponding to the xyYCC color space has been modified by the operator as an example. (1) A backlight of good color purity using RGB3 primary colors, and (2) Continuous dimming using complementary colors in RGB3 primary colors. Filter (micro-color filter) and so on. As a representative method of (1), an LED is used to optimize the light emission wavelength of the phosphor used in the cold cathode tube, and (2) a continuous dimming filter of yellow and cyan is used. Mirror (refer to Patent Documents 1 and 2). In this way, the factor that governs the color reproducibility of the LCD is a member that is related to light emission or a member that absorbs in the visible wavelength region, but is polarized to absorb light in the visible light wavelength region. And Lu, the status quo is not yet fully researched. In order to correspond to the xyYCC expansion Xin Yun p bow, on # #北,上,+ + 1m巴,, according to the improvement of the backlight or continuous dimming filter, it must be improved that the ia 1 and J shoulders are located in the visible light. Short wave at both ends

Characteristics of long and long wavelength regions. However, the conventional polarizer has the following threshold. You are asked to scream because the optical prefecture such as the absorbance or dichroism in the visible light wavelength region is extremely unstable, so the contrast ratio at a specific wavelength or color is lowered. Hanbie 3 m ^ ^ ^ ^ Knowing the color, because the color of the complementary color, that is, the short-wavelength region (380 nm to 500 nm) - Luogong / _ β), the color purity is low, so the color purity of blue light IV , color reproducibility cannot be fully obtained. Also, in the case of the expansion color space, it is widely g; the alliance #ra ^, c^ ^ ^, and the member is not in the case of the LCD projector or the vehicle LCD panel, because of the ancient, wu back, the dish Durability problem, so use non-iodine with dichroic dyeing 一 一 一 一 , , , , , , 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 The width of the J* vehicle is smaller than the color having absorption at a long wavelength: 歹笙:,: obtaining a sufficient aspect ratio necessary for the dichroic dye; Color chromaticity eve sleeve Γ Γ Γ Γ Γ ' Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ : : : : : : : The defect of the cause, and the modified polyvinyl alcohol (the combination of the two types of polychromatic materials and the coloring matter): the molecular material and the II II ^ ^ ^ heart are important, and therefore the industry expects to develop new a one-color pigment. Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-73290 [Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-25285] SUMMARY OF THE INVENTION The subject of the present invention is to provide a broadcast of a wide range of colors = useful for short wavelength regions (10) - _ In the case of the organic pigment of the anisotropic pigment film, the object of the present invention is to provide an organic dye for an anisotropic coloring boat which is excellent in durability. The pigment, which is characterized by the following formula (1), represents the form of the free acid.

312XP / invention manual (supplement) / 96-11/96119266

8 0) 200815533 In the formula (1), A1 and A2 each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or which is represented by the following formula (1-a) The basis. X represents any one selected from the following formulas (1-a) to (j-c). [Chemical 2] soil

(1 or or) p9 (1Γ) where π and Ql2 each independently represent an oxygen atom or a group. R and R each independently represent a hydrogen atom, an alkyl group which may have a substituent, and an amine group which may have a substituent. It can also be combined with r92 to form ruthenium. [化3] ^ -Ar1—^N—X2—at2-

Cl-a) a#

312ΧΡ/发明发明(补件)/96-11/96119266 200815533 In the formula U-a)~(i-c), χ2~χ4 each independently represent a -CH2 group or a c〇 group. Y1 to Y5 each independently represent a hydrogen atom, a fluorenyl group or an ethyl group. Ar!~Ar6 independently represent 丨, 4-phenylene, 14-anthranyl, anthracene, 5-naphthyl, 2'6-nene or a group represented by the following formula (i-ai) The 4-phenylene group, the 1,4-naphthyl group, the 1,5-anthranyl group, the 2,6-anthranyl group, and the group represented by the following formula (i-ai) may have a substituent. (l'al) In the formula (1-al), the ring α is a heterocyclic ring of 5 or 6 membered rings. In the monoazo dye for an anisotropic dye film according to the second aspect of the invention, the form of the free acid is represented by the following formula (2). [Chemical 5]

m In the formula (2), the A group may not have a stupid naphthyl group having a substituent, and the aromatic group having a substituent may have a substituent U-phantom group. There is no "base" or the following formula 3 ί2 ΧΡ / invention specification (supplement) / 96-11/96119266 10 200815533 X7 represents -CH2- group or -C0- group. Y represents a hydrogen atom, a thiol group or an ethyl group. ～R15 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, a sulfonic acid group, a trans group, a nitro group or a Wei group.

Ar21 represents iota, 4-phenylene, if-naphthyl, u-naphthyl, 2,6-naphthyl or a group represented by the following formula (1-a2).丨, 4-phenylene, 14-anthranyl, 1,5-anthranyl, 2,6-anthranyl, and a group represented by the following formula (1-a2) may have a substituent. [Chemical 6]

~GW (1 one no) In the formula (1 cold), Q and Q14 each independently represent an oxygen atom or a base. R and R94 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amine group which may have a substituent. ^ can also be combined with R94 [Chemical Formula 7] In the formula (l-a2), the ring stone is a heterocyclic ring of 5 or 6 membered rings. [Embodiment] 312XP/^_ Mingshu (Supplement)/96-11/96119266 π 200815533 Through the present invention, an anisotropic pigment film such as a polarizing film can be provided for right-handed use in a short-wavelength region (380 nmn~ 5〇〇μ) Organic pigments with excellent color properties.彳 The following describes the embodiment of the anisotropic pigment film of the present invention in detail. The description of the constituent elements of the present invention is the embodiment of the present invention (representative example), and the present invention is not limited to the contents. In the present invention, the term "anisotropy pigment film" refers to an anisotropic tenth pigment in the electromagnetic properties of any two directions selected from the pigmentation direction and the arbitrary two-dimensional stereo coordinates in the vertical plane. membrane. Electromagnetic properties, can be wrapped _ _ _, y, J, absorbing, absorbing, refraction and other optical properties, pen resistance, electric valley and other electrical properties. For example, there are rabbits and films which absorb absorption and refraction, such as linear polarized conductive anisotropic films. The domain, the retardation film, and the dye film in the present invention mean a layer containing a low molecular material and/or a polymer material: Example 2: a layer composed of a pigment. j 苟惶 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本As the functional film of the main effect, it is more preferable to use it for a polarizing film.

Furthermore, in the present invention, the heart of Shishi I. It is understood that it may have a substituent, meaning that there may be one or two or more substituents. /, [1] Embodiment 1 [Expression of free acid form by formula (1), azo dye for anisotropic pigment film] 312XP / invention manual (supplement) / 96-11/96119266 12 200815533 The azo dye used for the anisotropic pigment film of the first aspect of the present invention is characterized in that the free acid form is represented by the following formula (1). In the following, will be [Chemical 8]

Ji-A2 (1) /βχΐ——Μ

In the formula (1), Α and Α 2 each independently represent a phenyl group which may have a substituent, a neken group which may have a substituent, an aromatic heterocyclic group which may have a substituent or a formula (1-α) The base of expression. Χι denotes any one selected from the following formula ^~(1). [Chemistry 9]

-GH

a?) In the formula (1 α), Q and Q each independently represent an oxygen atom or a thio group. R91 and R92 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amine group which may have a substituent. R91 and R92 may also combine to form a ring. [Chem. 10], 312XP / invention manual (supplement) / 96-11/96119266 13 200815533

X2 — Ar2

-Η~X3—Ar4~)(4 一Ν,Αι^—(I-b)

In the formulae (l-a) to U-c), X2 to X4 each independently represent a _CH2_ group or a -C0- group. Y1 to Y5 each independently represent a hydrogen atom, a fluorenyl group or an ethyl group. ～Ar6 independently represents a 1,4-phenylene group, a 1,4-anthracenyl group, an anthracene group, a 2,6-anthranyl group or a group represented by the following formula (111). 1,4_Extension&amp;#, 1,4-naphthyl, 1,5-anthranyl, 2,6-extension, and the group represented by the following (l-al) may have a substituent. ^ [Chemical 11] _1 &gt; © O-al) The 'ring' is a 5 or 6 member ring. {Α1 and Α2} 312ΧΡ/Invention Manual (Supplement 196112266 200815533 <Phenyl group> When A1 and A2 are a phenyl group which may have a substituent, the phenyl group may have a substituent, and a sulfonic acid group may be mentioned. , a carboxyl group, a hydroxyl group, a nitro group, an alkoxy group which may have a substituent, an amine group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an amine methyl fluorenyl group which may have a substituent And an arylsulfonyl group which may have a substituent, a phenyl group which may have a substituent, an aryloxy group which may have a substituent, etc. The alkoxy group which is a substituent is usually 1 or more, and usually 6 or less. Preferably, it is 4 or less. Examples of the group which can be substituted on the base include an alkoxy group, a hydroxyl group, a dentate atom, a sulfonic acid group, a carboxyl group, etc. Specific examples of the alkoxy group include: Alkoxy group which may have a substituent such as a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group, a 2,3-dihydroxypropoxy group, etc., especially a lower group which may have a substituent The alkoxy group is preferred. The amine group as a substituent is usually represented by φ, 2, 丽, RS1, 丽, I83, φ. And R83 each independently represent an alkyl group which may have a substituent, a phenyl group which may have a substituent or a fluorenyl group which may have a substituent. The alkyl group has a carbon number of usually 1 or more, usually 12 or less, preferably 1 The fluorenyl group is represented by -C0R84, and R84 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent. The number of carbon atoms of the group and the alkoxy group is usually i or more, and the number of carbon atoms is usually 6 or less, preferably 4 or less. The number of carbon atoms of the alkenyl group is usually at least or more, usually 12 or less, preferably 1 or less. As a group which can be substituted on the alkyl group, the alkoxy group, the alkenyl group and the phenyl group, the azane 312XP/invention specification (supplement ypM 1/96119266 15 200815533 ^ group: hydroxyl group, A sulfonic acid group, a carboxyl group, a halogen atom, etc. As a group which can be substituted on the alkyl group, the phenyl group or the fluorenyl group of R to R, a phenyl group, an alkoxy group or a hydroxyl group which may have a substituent may be mentioned. a sulfonic acid group, a carboxyl group, a halogen atom, etc., which may be substituted on the phenyl group, and may be mentioned - an alkyl group having 1 to 4 carbon atoms, an alkoxy group having a carbon number of 丨4, a sulfonic acid group, a carboxyl group, a hydroxyl group, etc. Specific examples of the amine group include an amine group, a methylamino group, and an ethylamine group. Base, 2, base ethyl | female group, 4-sulfophenylamino group, 4-carboxybenzhydrylamino group, anti-butenylamino group, etc. The number of carbon atoms of the alkyl group as a substituent It is usually 1 or more, usually 6 or less, preferably 4 or less. The group which can be substituted on the alkyl group may, for example, be a methoxy group, a substituent group, a halogen atom, a carboxylic acid group or a group. Specific examples of the alkyl group include a methyl group and an ethyl group, and particularly preferably a lower alkyl group which may have a substituent. The number of the substituents as a substituent is usually 1 or more, and usually 12 or less. It is preferably 10 or less. The group which may be substituted on the alkenyl group may, for example, be an alkyl group, a phenyl group or a carboxyl group. Specific examples of the alkenyl group include a trans-2-carboxyvinyl group and a trans-2-(2-cyanophenyl)ethene group. The amine carbenyl group as a substituent has a carbon number of usually 丨 or more, usually 6 or less, preferably 4 or less. Examples of the group which can be substituted on the amine mercapto group include a carbon group having 1 to 4 carbon atoms which may be substituted. Specific examples of the amine methyl sulfhydryl group which may have a substituent include an amine methyl group and an N-decylamine fluorenyl group. 312XP/Invention Manual (Supplement)/96-11/96119266 16 200815533 The aminesulfonyl group as a substituent has a carbon number of usually 丨 or more, usually 6 or less, preferably 4 or less. Examples of the group which can be carried out on the amine ruthenium group include a carbon group having 1 to 4 carbon atoms which can be substituted. Specific examples of the aminesulfonyl group which may have a substituent include an amine group and an N-methylamine group. The phenyl group as a substituent has a carbon number of usually 6 or more, usually u or less, preferably 8 or less. Examples of the group which may be substituted with the phenyl group include an alkoxy group, a hydroxyl group, a sulfonic acid group, and a carboxyl group. Specific examples thereof include a phenyl group which may have a substituent such as a phenyl group, a 3-sulfophenyl group or a 4-sulfophenyl group. — an aryl group constituting an aryloxy group as a substituent, preferably a phenyl group or a naphthyl group; and a substituent which may be present on the aryl group: a pyridyl group, a decyloxy group, a certain group, a rhein group, Jingji et al. Specific examples of the aryloxy group which may have a substituent include phenazine, naphthoquinone group, p-tolyloxy group, p-methoxyphenoxy group, benzylphenoxy group, and the like. When the phenyl group of A or A2 has a substituent, it may be substituted with a hydrophilic group such as a rhein group, an ester group or a mercapto group in either or both of the groups 2 or a2. It is better from a sexual point of view. Also, from the point of view of color. The number of substitutions of the amine group or the trans group which may have a substituent is preferably 2 or less. The phenyl group may have one or more such substituents, and may have two or more substituents; and the substituent is preferably three or less. The substitution position of the /hel substituent is substituted at the meta or para position with respect to the azo group, and is preferred because of high molecular linearity. <Naphthyl> When the fields A and A are a naphthyl group having a substituent, the naphthyl group may have a substituent of 312XP/invention specification (supplement)/96-11/96119266 17 200815533, and examples thereof include: an acid group. , a group, a thio group, a nitro group, an alkoxy group which may have a substituent, an amine group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an amine group which may have a substituent A brewing group, an aminesulfonyl group which may have a substituent, a phenyl group which may have a substituent, an aryloxy group which may have a substituent, and the like. ^ Specific examples of the substituent of the naphthyl group are the same as those of the above-mentioned substituent of the phenyl group.

When a naphthyl group of a! or a2 has a substituent, a hydrophilic group such as a repeating acid group, a silk or a (iv) is substituted in either or both of the plant or A2, and this is a viewpoint of solubility in water. The words are better. Further, from the viewpoint of color tone, the number of substitutions of the amine group or the group which may have a substituent is preferably one or less. The "base" which may have a substituent may have a substituent of two or more substituents, and may have two or more substituents, preferably four or less substituents, and preferably two or less. The substitution position of the side substituent is preferably substituted at the 2-position relative to the naphthyl group from the viewpoint of molecular linearity, and the other substituents are at the 1-, 4-, 5-, 6- or 7-position. It is better to replace it. On the other hand, in terms of color tone, the azo group is preferably relative to :::::, and the other substituents are substituted with an aromatic heterocyclic group at the 1-, 4- or 5-position. When A1 and the aromatic heterocyclic group which may have a substituent, there is no heterocyclic group, and it is preferably a group derived from a monocyclic or bicyclic quinone.

Ti = atom of abbrew: nitrogen atom, sulfur atom and milk atom m (tetra) ring group having a plurality of constituent rings other than carbon 312XP / stomach description (supplement) / 96-11/96119266 lg 200815533 atomic time These may or may not be the same. The 夭 π 3 〇 θ has no heterocyclic group, and when the carbon number U von 3 or more is usually an aromatic polycyclic aromatic hetero ring of 1 Å or less, the heterocyclic moiety is equine. ▲ is in combination with an azo group. U minus binding, hydrocarbon ring benzene = ^ base 'specifically, · base, sulfonyl, wow, = plug,, base, benzofluorenyl, radical, naphthylamine ^ base 111^1), ^基&quot;pyridonyl A, A may have a substituent of an aromatic heterocyclic ring = acid group, a group, a group, a nitro group, may have a substituent on the oxygen I, , and have a substitution Amino group, which may have a decyl group, may have a substituent, an amine group which may have a substituent, an amine group which may have a substituent, a phenyl group which may have a substituent, a cyano group Wait. Specific examples of the substituent of the aromatic heterocyclic group are the same as those of the specific examples of the substituent of the phenyl group. When the aromatic heterocyclic group of the field A or yttrium has a substituent, it may be substituted with a hydrophilic group such as a rhein group, a group or a group in either or both of the plant or a2, and this is a water-based From the viewpoint of solubility, it is preferred. Further, from the viewpoint of color tone, the number of substitutions of the amine group or the hydroxyl group which may have a substituent is preferably 2 or less. The aromatic heterocyclic group which may have a substituent may have one or more such substituents, and may have two or more substituents, preferably four or less substituents, more preferably two or less. <Bases expressed by the formula (l-α)> Α and Α may be groups represented by the above formula (1 - q). 312XW invention manual (supplement) /9641/96119266 19 200815533 [Chemistry 12]

(1 - Of) In the formula (1 α ), Q and Q each independently represent an oxygen atom or an aryl group. R91 and R92 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an amine group which may have a substituent. R91 and R92 may also combine to form a ring. In the formula (1 - α), the alkyl group which may have a substituent in R92, and the carbon number thereof is usually 1 or more, usually 6 or less, preferably 4 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulphate group or a carboxyl group. Specific examples of the alkyl group include a mercapto group, an ethyl group and the like, and particularly preferably a lower alkyl group which may have a substituent. The amine group which may have a substituent of R91 and R92 is usually represented by -NIj2, _-NHR211, -NR212R213. R2&quot;~r2&quot; each independently represents a phenyl group which may have a substituent, a phenyl group which may have a substituent, or a fluorenyl group which may have a substituent. The carbon number of the alkyl group is usually 1 or more, usually 12 or less, preferably 10 or less. The fluorenyl group is represented by -C0R214, and R214 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent. The alkyl group and the alkoxy group have a carbon number of usually 1 or more, usually 6 or less, preferably 4 or less. The number of carbon atoms of the alkenyl group is usually 1 or more, usually 12 or less, preferably 10 or less. The alkyl group, the alkoxy group, the alkenyl group and the phenyl group may be substituted by a group of 312XP/invention specification (supplement)/9641/96119266 20 200815533, and an alkoxy group, a hydroxyl group, a sulfonate may be mentioned. An acid group, a carboxyl group, a halogen atom or the like. a group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group of R 11 to R213, and may be a phenyl group, an alkyl group, an alkoxy group, a arylamino group, a thiol group or a fluorenyl group which may have a substituent. A yellow acid group, a thiol group, a halogen atom, and the like. The group which can be substituted with the phenyl group may, for example, be a sulfonic acid group, a carboxyl group or a hydroxyl group. Further, when * R is bonded to R 2 to form a ring, a substituent having a group having a carbonyl group, a thiocarbonyl group or the like as an amine group can be used. In the case of the formula (1α), it is preferred that the carbon number is 3 or more and 2 or less, and specific examples thereof include the following. [Chem. 13]

Mm <a preferred example of A1> and ^ is A1' is preferably one selected from the group consisting of one or two groups consisting of a decanoic acid group, a (four) group, and a hexyl group (tetra)oxy group. = phenyl or naphthyl. When the substituent is a plural, the substituent may be the same. And the base group and the naphthyl group ' may have a substituent other than the above substituent, and when the substituent is '3', the phenyl group or the naphthyl group, and the substituent which is 11 / or same. 312XP/Invention Manual (Repair) Grab i 1/96119266 21 200815533 2 When the phenyl group has a substituent, it is preferably bonded to the green with respect to the azo group. Further, the naphthyl group is preferably an azo group bonded to the 2-position of the naphthalene ring, and has a substituent at the 5-position and the 6-position 哎7-position when it has a substituent in the A. It is better. 4 times, <Preferred Example of A2> D: Comparative: a phenyl group which may have a substituent or a fluorene group which may have a substituent. The aromatic heterocyclic group can be particularly preferably exemplified by a bite base, a sulfonyl group, a 嗟 基 & 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比Base. The substituent which is hydrazine is preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, a phenyl group which may have a substituent, a nitro group, a hydroxyl group, a carboxyl group Or a sulfonic acid group. #八中 In terms of solubility in water, interaction with substrate or durability, a, preferably a thiol, a mineral acid group, a thiol group, a methyl group, a methoxy group, an ethoxy group, 2, 3-Dihydroxypropoxy, 3-sulfophenyl, 4-sulfophenyl, aminyl, methylamino or an amine substituted by a thiol group. U1} and X are not selected from any of the following formulae (1aa) to (1c), but in the formulae (1-a) to (1-c), it is preferred to (1-a) indicates the basis. That is, in (1 - 1 to (1 - C), since the base connecting the two azo groups is short, the entire molecule is easily obtained in a straight line structure, so (1 - a) is preferable. [Chem. 14] 312XP/ Invention specification (supplement)/96]1/96119266 22 200815533

(l-a) &quot;Άγ3* X k fH3 ψο policy -Q _|y^rg_'

0 ") &lt;x2 to x4&gt; base or -C0-group X2 to X4 are each independently represented by -d <Y1 to Y5&gt; Y to Y each independently represent a hydrogen atom, a methyl group or an ethyl group. <Ar1~Ar6&gt;

Ar1 to Ar6 each independently represent 1&gt;4_phenylene, anthracenyl, n-indenyl-naphthyl-naphthyl or a group represented by the following formula (1)(1). The phenyl group, the 1'4-naphthyl group, the U-naphthyl group, the 2, (1) Shen Caiji, and the group represented by the following formula (Ι-al) may have a substituent. [化15]

(1^1) In the formula (l-al), the ring α is a heterocyclic ring of 5 or 6 membered rings 312ΧΡ/invention specification (supplement)/96-11/96119266 23 200815533 ring α and formula (l-al) The benzene rings combine to form a condensed ring. , the X ', and the ring group may, for example, be a quinoline decyl group, an isoquinoline fluorenyl group, a benzthiadiazole fluorenyl group, an phthalimide diamine fluorenyl group, and the like. It is to be noted that, as shown in the formula (Ι-al), the linking position is located at a mutual base of the benzene ring portion. <Substituent of Ar1 to Ar6> The base group may be an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, an _, a 素 atom, and a feldspar I group, 1 hydroxyl group. In terms of molecular linearity or solubility in water, preferred hydrazine, Ar~Ar6 does not have a substituent, or has a methyl group, a methoxy group, a 2,3-monopyridyloxy group, a carboxyl group, a sulfonic acid group. A group, a fluorine atom, an amine group or an ethenylamino group is used as a substituent.

Ar to Ar may have one or more such substituents, and may have two or more such substituents. However, the substituent is preferably three or less, more preferably two or less. When there are two or more such substituents, the substituent is preferably substituted at the adjacent original φ. Specific examples of the substituent which Ar1 to Ar6 may have are exemplified below. The number of carbon atoms of the alkyl group is usually 1 or more, usually 6 or less, preferably 4 or less, more preferably 3 or less. The group which can be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkyl group include a mercapto group and an ethyl group, and particularly preferably a lower alkyl group which may have a substituent. The number of carbon atoms of the alkoxy group is usually 1 or more, usually 6 or less, preferably 4 or less, more preferably 3 or less. The group which can be substituted on the alkoxy group can be exemplified by activating alkoxy group, a hydroxyl group, a dentate atom, a rhein group, a carboxyl group and the like, in 312XP/invention specification (supplement)/96-11/96119266 24 200815533. Specific examples of the alkoxy group include an alkyl group which may have a substituent such as a decyloxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group, or a 2,3-dihydroxypropoxy group. The oxy group is particularly preferably a lower alkoxy group which may have a substituent.

The amine group is usually represented by -NH2, -NHRa, -NW, and R«~Rr each independently represents an alkyl group which may have a substituent, a phenyl group which may have a substituent or a fluorenyl group which may have a substituent. The number of carbon atoms of the alkyl group is usually 丨 or more, usually 4 or less, preferably 2 or less. The fluorenyl group is represented by _c 〇 r5, and v represents a decyl group which may have a substituent, an alkoxy group which may have a substituent or a phenyl group which may have a substituent. The carbon number of the filament and the filament base is usually 1 or more, usually 4 or less, preferably 2 or less. Examples of the group which can be substituted on the alkyl group, the money group and the phenyl group include an alkoxy group, a hydroxyl group, a amic acid group, a slow group, and a halogen atom. Examples of the group which can be substituted with a phenyl group or a phenyl group or a phenyl group are an alkoxy group, a hydroxyl group, a syllabic group, a carboxyl group, a halogen atom and the like. Specific examples of the amine group include an amine group, a methylamino group, an ethylamine group, a propylamine amine group, a phenylamine group, an ethylamine group, and a benzoylamino group. Such as self-priming atoms, can be exemplified: fluorine material, chlorine material, _ sub, moth atom

Preferred examples of Ar6 &lt;Ar&gt; and: taking ~: two', in terms of molecular linearity or hue, it is preferably substituted with 1,4_phenylene or 1&gt;4_ or has Preferred substituents described below. Ding soil x soil white, 疋 no action ", the preferred material has a substituent 5,8_ material two counties, n 31 Qing Ming instructions (suggested purchase Gu 25 25151515 stretch phenyl or 1,4-yinaki As Ar2, a 1,4-phenylene group which may have a substituent is preferred.

The substituent of Ar Ar is preferably an alkyl group having a carbon number of usually 1 to 4 which may have a substituent, an alkoxy group having a carbon number which may have a substituent of usually 丨 to *, an amine group which may have a substituent, A tartaric acid group, a dentate atom or a thiol atom. In terms of molecular linearity or solubility in water, the substituent is a methyl group, a thiol group, a 2,3-dihydroxypropoxy group, a sulfonic acid group, a fluorine atom, an amine group or an acetamino group. good. Lu may have one or more such substituents, and may have two or more such substituents, preferably three or less, more preferably two or less. When having two or more substituents, it is preferred that the substituent be substituted on an adjacent atom other than the ring. {Molecular weight} The molecular weight of the dye (1) is preferably 18 Å or less in terms of free acid form, preferably 1,500 or less, more preferably 13 Å or less, and 12 Å to φ. It is best to use 1100 or less. [Azo dye for an anisotropic dye film of a free acid form in the formula (1-1)] The above dye (1), which is a free acid form, is preferably represented by the following formula (dipor). Hereinafter, the azo dye for an anisotropic dye film in the form of a free acid is represented by the following formula (1_υ) as a "pigment (1 - 1). 312 ΧΡ / invention specification (Supplement 乂外-丨1/96119266 26 200815533 [Chemical 16] Good one wide production -

_N 阙{A21} In the formula (li), A represents a group selected from the group consisting of one or two alkoxy groups which are a sulfonic acid group, a slow group and a substituent which may have a substituent as a substituent thereof. Phenyl or naphthalene | When the substituent is # number of _, the substituents may be the same or different. &lt;Specific Example of Substituent of A21&gt; The substituent which may have an alkoxy group of the substituent is exemplified by a substituent which the V and A? are phenyl groups, and may have a substituent Specific examples of the alkoxy group are the same.

The phenyl group or the naphthalene I may have a substituent other than the above substituent. The substituent " at this time" is exemplified by the substituent which the above-mentioned plant and a2 are a phenyl group or a naphthyl group, and a methyl group, a hydroxyl group, etc. are preferable. <Substitution position> The substituent of the phenyl group of '&quot; soil 'A is preferably bonded at the 3 or 4 position with respect to the azo group. Further, the naphthyl group of A is preferably an azo group bonded to the 2-position of the naphthalene ring, and preferably has a substituent at the 6-position or the 7-position. {A22} is a phenyl group which may have a substituent or may have a substituent. 312XP / Inventive Specification (Supplement) / 96-11/96119266 27 200815533 Heterocyclic group. The aromatic heterocyclic group which may have a substituent is preferably a group derived from a monobicyclic ring as a color having absorption in a short-wavelength region; and a color, ==== ring is particularly preferred. Examples of the atom constituting the aromatic heterocyclic ring include a nitrogen material, a sulfur material, and an oxygen material. When the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, the same may be different. The aromatic heterocyclic group is preferably an aromatic heterocyclic group having 3 or more and 1 or less carbon atoms. When it is a polycyclic aromatic (tetra) heterocyclic ring, the heterocyclic moiety can be directly bonded to the azo group, and the tobacco ring moiety can be bonded to the azo group. Specific examples of the aromatic heterocyclic group include a κ group, a material group, a material group, a decyl group, a benzopyrazolyl group, a quinolinone group, a pyrazolyl group, and a pyridone group. The substituent of the earth &lt;A22> The phenyl group and the aromatic heterocyclic group may have a substituent, and an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent may be mentioned. An amine group, a phenyl group, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a repeating acid group which may have a substituent. Specific examples of the substituent which A22 may have are exemplified below. The number of carbon atoms of the alkyl group is usually 1 or more, usually 4 or less, preferably 3 or less. Examples of the group which can be substituted on the alkyl group include an alkoxy group, a light group, a dentate atom, a sulfonic acid group, and a carboxyl group. Specific examples of the alkyl group include a methyl group, an ethyl group and the like, and particularly preferably a lower alkyl group which may have a substituent. The number of carbon atoms of the alkoxy group is usually 1 or more, usually 4 or less, preferably 3 or less. The group which can be substituted on the alkoxy group may, for example, be an alkoxy group, 312XP/invention specification (supplement)/96-11/96119266 28 200815533 a hydroxyl group, a dentate atom, a sulfonic acid group, a carboxyl group or the like. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a ethoxy group, a 2, 3-dihydroxypropoxy group, etc., which may have a substituent. The alkoxy group is particularly preferably a lower alkoxy group which may have a substituent. The amine group is usually represented by -Li 2, -Li Wei, -Li bRe. Γ~Γ respectively An alkyl group which may not have a substituent, a phenyl group which may have a substituent or a fluorenyl group which may have a substituent. The number of carbon atoms of the alkyl group is usually 丨 or more, usually 12 or less, preferably _ 10 or less. The fluorenyl group is represented by -C〇Rd, and represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent. The carbon number of the alkyl group and the alkoxy group is usually 1 or more, usually 6 or less, preferably 4 or less. The number of carbon atoms of the alkenyl group is usually 1 or more, usually 12 or less, preferably 1 or less. The group which may be substituted on the alkyl group, the alkoxy group, the alkenyl group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. The group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group of Ra to Re may, for example, be a phenyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a functional atom which may have a substituent. The group which may be substituted on the phenyl group may, for example, be a rhein group, a thiol group or a thiol group. Specific examples of the amine group include an amine group, a methylamino group, an ethylamino group, a 2-diazetoethylamine group, a 4-sulfophenylamino group, a 4-carboxybenzylideneamino group, and a transbutene group. Mercaptoamine and the like. When the phenyl group has a substituent, the carbon number including the substituent thereof is also 312XP/invention specification (supplement)/96_11/96119266 29 200815533 L苇 is 6 or more, and the amount is ι〇 or less, preferably 8 or less. Examples of the group which can be substituted on the phenyl group include an alkoxy group, a hydroxyl group, a sulfonic acid f, and a carboxyl group. Specific examples thereof include a phenyl group which may have a substituent such as a phenyl group, a 3-sulfophenyl group or a 4-sulfophenyl group. The substituent of Λ 22 is preferably a hydroxyl group, a sulfonic acid group, a carboxyl group, a methyl group, an oxo group or an ethoxy group from the viewpoints of solubility in water, interaction with a substrate, or durability. 2, 3-dihydroxypropoxy, 3-sulfophenyl, 4-stone, phenyl, amino, methylamino, or an amine substituted by a thiol group.

Ar1, Ar2, X2&amp; γ* are respectively synonymous with the above formula (1_a). <Ar1, Αγ2>

ArJ is a phenyl group which may have a substituent, a 1,4-naphthyl group which may have a substituent, or a 5,8-anthracene group which may have a substituent. a substituent having a substituent ' or having a carbon number which may have a substituent, a cal group of 1 to 4, a carbon number which may have a substituent is usually u 4 = an amine group having a substituent, a sulfonic acid group or a hydroxyl group as its The substituent is t. In terms of molecular linearity or solubility in water, it has a substituent, or has a methyl group, a methoxy group, a 2,3-di-propylpropoxy acid group or an ethylamine group as a substituent thereof. Especially good. Further, two or more of these substituents may have two or more such substituents, but the substituent is preferably at least 12 or less. When there are two or more such substituents other than the ruthenium atom, substitution is preferably carried out at the substitution. Listen to neighboring atoms that are not in the nucleus

Ar2' is preferably a substitutable 1,4-phenylene group from the viewpoint of molecular linearity or color tone; Ar2 has no substituent, or has a 312XP/invention specification (supplement)/96· 11/96119266 200815533 The base, mouse atom, and glucomannan may have one such amine group as the substituent thereof, preferably less than 3 3: 3, but may have 2 or more substituents, , i generation ^ the following is especially good. It is preferable to have two or more such "heart 2" = adjacent atoms which are not in the ring. ...Ar may be the same or different. &lt;X2, Y1> Group X. The group or n γι is preferably a hydrogen atom. Or A. {Formula (Bu-1)} Among the above-mentioned dyes (1-1), an anisotropic dye film represented by a free acid form is preferably an azo dye. [Chem. 17]

&lt;α21&gt; Α21 is synonymous with the formula (1-1). <R21 to R24> R to R each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, an I atom aureole group or a warp group. 312XP/Invention Manual (Supplement)/96-11/96119266 31 200815533 Specific examples of R to R4 include the following. The alkyl group of R to R24 has a carbon number of usually i or more, usually 4 or less, and (d) is a squat. The base to be substituted on the base of the hospital may be exemplified by a emulsifier base, a thiol group, an i atom atom, a (tetra) group, and a county. Specific examples of the silk include a methyl group and an ethyl group, and particularly preferably a lower alkyl group which may have a substituent. The alkoxy group of ? R has a carbon number of usually 1 or more, usually 4 or less, preferably 3 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a spectrin atom, a rhein group or a slow group. Specific examples of the alkoxy group include an alkyl group which may have a substituent such as a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group or a 2,3-dihydroxypropoxy group. The oxy group is particularly preferably a lower alkoxy group which may have a substituent. The amine group of R to R24 is usually represented by -Li 2, -Li, -NRfRg, and Re to Rg each independently represent an alkyl group which may have a substituent, a phenyl group which may have a substituent or a mercapto group which may have a substituent . φ The number of carbon atoms of the alkyl group is usually 1 or more, usually 4 or less, preferably 2 or less. The fluorenyl group is represented by -C0Rh, and Rh represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a phenyl group which may have a substituent. The carbon number of the alkyl group and the alkoxy group is usually 1 or more, usually 4 or less, preferably 2 or less. The group which may be substituted with the alkyl group, the alkoxy group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. The group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom 312XP/invention specification (supplement)/96·11/ 96119266 32 200815533 and so on. Specific examples of the amine group of R21 to R24 include an amine group, a decylamino group, an ethylamine group, a propylamino group, a dimethylamino group, a phenylamino group, and an ethylamino group: a mercaptoamine group. R to R 2 'in terms of molecular linearity or solubility in water, hydrogen atom, sulfhydryl group, decyloxy group, 2,3-di-propylpropoxy group, sulfonic acid group or ethyl group good. Further, R23 to R2S are preferably a hydrogen atom, a fluorine atom, an amine group, an ethenylamino group or a fluorenyl group from the viewpoint of molecular linearity or color tone. Further, in the formula (1-1-1), the substituents other than the hydrogen atom may be contained in the range of F to R24, and may be two or more, preferably three or less, or two or less. Especially good. When there are two or more such substituents other than a hydrogen atom, it is preferred that the substituent be substituted at an adjacent atom other than the ring. &lt;R25, R26&gt; R25 and R26 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, a trans group, a carboxyl group or a sulfonic acid group. The alkyl group of R 5 and r26 has a carbon number of usually 丨 or more, usually 4 or less, preferably 3 or less. Examples of the group which can be substituted with the alkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group, and a carboxyl group. The alkyl group may, for example, be a mercapto group or an ethyl group, and particularly preferably a lower alkyl group which may have a substituent. The alkoxy groups of R and R26 have a carbon number of usually 1 or more, usually 4 or less, preferably 3 or less. As a group which can be substituted on the alkoxy group, 312 ΧΡ / invention specification (supplement) / 96-11/96119266 33 200815533, which may be exemplified by a 4-oxy group, a thiol group, a sulfonyl group, a rhein group, and an ester group. Wait. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group, a 2,3-dihydroxypropoxy group, etc., which may have a substituent. The alkoxy group is particularly preferably a lower alkoxy group which may have a substituent. The amine groups of R and R are usually represented by - Li 2, - Li Rk, -. R, Rm and Rn each independently represent an alkyl group which may have a substituent, a phenyl group which may have a substituent or a fluorenyl group which may have a substituent. The number of the sulphur base is usually 1 or more 'usually 4 or less, preferably 3 10 or less. The fluorenyl group is represented by -C0Rp, and rp represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a phenyl group which may have a substituent. The number of carbon atoms of the alkyl group and the alkoxy group is usually 1 or more, usually 4 or less, and more preferably 2 or less. The alkyl group, the alkoxy group and the phenyl group may be substituted, and examples thereof include an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, and a halogen atom. Φ The group which can be substituted on the alkyl group of R, R, and Rn, the phenyl group, and the aryl group, and examples thereof include an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, and a halogen atom. Specific examples of the amine group of R25 and R26 include an amine group, a decylamino group, an ethylamine group, a 2-Distylethylamino group, and a 3-Deltylphenylamino group. R25 and R26' are preferably a hydrogen atom, a decyl group, a methoxy group, an ethoxy group, a 2,3-dihydroxypropoxy group, a carboxyl group or an acid group in terms of molecular linearity or solubility in water. &lt;R27&gt; R27 represents a halogen atom, a nitro group, an alkoxy group which may have a substituent, a hydroxyl group, 312XP/invention specification (supplement)/96-11/96119266 34 200815533 or an amine group which may have a substituent. In the seventh aspect, it is preferred that any of R25 to IT is a group other than a hydrogen atom. The alkoxy group of R has a carbon number of usually m, usually 4 or less, more preferably 3 or less. Specific examples of the group which can be substituted on the alkoxy group include an alkoxy group, a transatom group, a halogen atom, a rhein group, and a second example, and examples thereof include a methoxy group and an ethoxy group. An alkoxy group which may have a substituent such as a n-propoxyoxy group, a hydroxyethoxy group, a 2,3-dihydroxypropoxy group or the like, and particularly preferably a lower alkoxy group which may have a substituent. • The amine group of R27, usually expressed as -leg 2, -NHr, -NRsr. r to R) each independently represents an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a brewing group which may have a substituent. The carbon number of the alkyl group is usually 1 or more, usually 12 or less, preferably 10 or less. The fluorenyl group is represented by -C0Ru, and Γ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent. The carbon number of the alkyl group and the alkoxy group is usually 1 or more, usually 6 or less, preferably 4 or less. The number of carbon atoms of the alkenyl group is 1 or more, usually 12 or less, preferably 1 or less. The alkyl group, the alkoxy group, the alkenyl group and the group substituted on the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. The group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group may, for example, be a substituent group, an alkoxy group, a trans group, a repeating acid group, a substituent or a halogen atom. The group which can be substituted on the phenyl group is 312 ΧΡ / invention specification (supplement) / 96-11/96119266 35 200815533 sulfonate group, carboxyl group, hydroxyl group and the like. Specific examples of the amine group of R27 include an amine group, a methylamino group, an ethylamino group, a carboxymethylamino group, a 2-sulfoethylamino group, a 4-sulfophenylamino group, and 2, 3- Dihydroxypropylamino, 3-sulfophenylamino, etidylamino, benzhydrylamine, 4-rebase, or tert-butylamino. R27 is an alkoxy group having a water-soluble group such as a hydroxyl group, a sulfonic acid group or a carboxyl group as a substituent in terms of solubility in water, interaction with a substrate, or durability, and has the water-soluble group as a substituent. The substituted amino group, the benzhydryl fluorenylamino group, the amine group, the methylamino group, and the hydroxy group are preferred; and the amine group, the methylamino group and the hydroxy group are particularly preferred. {Formula (1-1-2)} Among the above-mentioned dyes (1-1), an anisotropic dye film represented by the following formula (丨-〗 2) is preferably an azo dye. [Chem. 18]

olOS

A is synonymous with the formula (1-1). &lt;R101 to R104&gt; R1 〇1 to p 1 〇4, and the cleavage independently represents a hydrogen atom, a group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, and fluorine Atom, sulfonic acid group or hydroxyl group. Side invention specification (supplement purchase 1%%1 crane 36 200815533 &gt;101

R 104 is also synonymous with R21 to R24 in the formula U - H), preferably not a hydrogen atom, an alkyl group which may have a substituent, an amine group having a substituent, a mercapto group, a rebellion of 5 and R1G6 each independently represents an alkoxy group or a sulfonic acid group which may have a substituent. R105 and R1.6 are the same as those in the formula (1-diindole). • R25 and R26 of R107 are synonymous, and preferably R also represents a hydrogen atom, a nitro group, an alkoxy group which may have a substituent, and a hydroxyl group. Or an amine group which may have a substituent. Among them, it is preferred that any of R to R is a group other than a hydrogen atom. R107 is synonymous with R27 in the formula (1-1 -1), preferably also The same is true. &lt;Y&quot;&gt; Υ denotes a hydrogen atom or a sulfhydryl group. {Molecular weight} The molecular weight of the pigment (1 -1) is preferably 1,500 or less in terms of the free acid form, more preferably 1200 or less. [Azo dye for an anisotropic dye film of a free acid form in the formula (1 - 2)] The above-mentioned dye (1) is preferably a free acid form represented by the following formula (1-2). The formula (1-2) indicates that the azo dye used for the anisotropic dye film in the free acid form is referred to as "pigment (1-2)". 312ΧΡ/Invention Manual (Supplement)/96-11/96119266 37 200815533 19]

Ar1 A3t—N&quot; (1-2) {Ar1 and Ar2}

Ar^Ar2 is synonymous with the formula (η). U31 and A32} A. 31 and A32 each independently represent a compound of the following formula (i.e., 叫20) 〇21 (l^a) In the formula (1-2a), the ring G1 may have a substituent other than -0Z1. Zl Lu 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. <Z1> An alkyl group which may have a substituent in Z1, and is an alkyl group having a carbon number of usually 1 or more and 6 or less, preferably 3 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group or a phenyl group which may have a substituent (the substituent may be an alkyl group having 1 to 4 carbon atoms, and a carbon number of 1) ～4 alkoxy group, sulfonic acid group, carboxyl group, etc.), a halogen atom, a sulfonic acid group, a carboxyl group, and the like. Examples of the alkyl group include a methyl group and an ethyl group. 312XP/Invention Manual (Supplement)/96-11/96119266 38 200815533 The group which may be substituted on the phenyl group which may have a substituent, and the alkyl group which may have a substituent (this substituent, Examples thereof include an alkyl group having a carbon number of 44 to 4, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and a carboxyl group, an alkoxy group, a carboxyl group, a sulfonic acid group, and a hydroxyl group. Specific examples of the phenyl group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, and an o-carboxyphenyl group. <Substituent of Ring G1> The substituent which the 裱G1 may have may be a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and may have a ^^ The amine group of the substituent. Ring G1 may have one or more of these substituents, and more than one of these substituents. Specific examples of the substituent of the ring G1 are as follows. The alkyl group which may have such a substituent is an alkyl group having a carbon number of usually hereinafter or more, 6 or less, preferably 3 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkyl group include a mercapto group, an ethyl group and the like, and particularly preferably a substituent having a lower alkyl group. The alkoxy group which may have such a substituent is a methoxy group having a carbon number of usually 1 or more, 4 or less, and a parent of 3 or less. The substituent which may be substituted on the alkoxy group may, for example, be an alkoxy group, a thiol atom, a dentate atom, a carboxylic acid group or a thiol group. Specific examples of the alkoxy group include an alkyl group which may have a substituent such as a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group or a 2,3-dihydroxypropoxy group. The oxy group is particularly preferably a lower alkoxy group which may have a substituent. The amine group which may have such a substituent is usually represented by -Li 2, - NHRV, -NRWRX, 312 ΧΡ / invention specification (supplement) / 96-11/96119266 39 200815533 - Li C0Ry, "~Ry respectively represent An alkyl group having a substituent or a phenyl group which may have a substituent. The number of carbon atoms of the alkyl group is usually i or more, usually 4 or less, preferably 2 or less. The group which may be substituted on the alkyl group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. Specific examples of the amine group include a methylamino group, an ethylamino group, a propylamino group, a dimethylamino group, a phenylamino group, an ethenylamino group, and a benzhydrylamino group. In the formula /l-2b), the ring G2 may have a substituent other than _NZ2Z3. Z2 and Z3 each independently represent a hydrogen atom, a carbon group having 1 to 6 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. &lt;z2 and z3&gt;

And hydrazine each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. ^ As the substituent which the phenyl group and the phenyl group may have, a phenyl group which may have a substituent, a hydroxy group, and a substituent may be mentioned, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms. The carbon number is 1 to 4, and the sulfonyl group, the sulphate group, the carboxyl group, etc., the _ atom, the sulfonic acid group, and the carboxyl group are used. The same is true for the alkyl group of the specific example when Ζ1 and Ζ are alkyl groups which may have a substituent.

The ring G2 may have a substituent other than the milk 3, and is the same as exemplified as the substituent of the upper G. 12XP/^^^^i(ffifr)/96-l 1/96119266 40 200815533 [Chem. 22]

(l-2c) In the formula (l-2c), Z5 and Z7 each independently represent a hydrogen atom or a group of 1 to 6 which may have a substituent. Z represents a hydrogen atom, a repeating acid group, a cyano group, an amine sulfhydryl group, a carboxyl group, a sulfomethyl group or a carboxymethyl group. Soil A specific example in the case where Z and Z are a base group which may have a substituent, and is the same as the alkyl group of the above Z1. [Chem. 23]

(l-2d) In the formula (l-2d), Z represents a methyl group, a carboxyl group or an alkoxycarbonyl group having 2 to 4 carbon atoms. Z9 and Z1G independently represent a ruthenium atom or a sulfonic acid group. Specific examples of the case where Z is an alkoxycarbonyl group having 2 to 4 slaves include a methoxycarbonyl group and an ethoxycarbonyl group. · 312XP/Invention Manual (supplement)/96-11/96119266 i 200815533 [Chem. 24]

(1 * 2 苟) In the formula (l-2e), 'Z11' represents a hydrogen atom or an alkyl group having a carbon number of J to 6 which may have a substituent. Z12 represents a hydrogen atom or a sulfonic acid group. A specific example when Zu is an alkyl group which may have a substituent is the same as the alkyl group of the above oxime 1. [Chem. 25]

In the formula (1-2f), Z13 and Z14 each independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms which may have a substituent, and a carbon number of 1 to 4 which may have a substituent. The alkoxy group or a mercaptoamine group having 1 to 7 carbon atoms which may have a substituent. When Z13 and Z14 are an alkyl group which may have a substituent, the alkyl group may have a substituent, and usually has a carbon number of 1 or more, 4 or less, preferably 3 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, 312 ΧΡ/invention specification (supplement)/96-11/96119266 42 200815533 a phenyl group which may have a substituent (the substituent may be used Examples thereof include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having a % of 1 to 4, a carboxylic acid group, and a carboxyl group, and the like, a dentate atom, a sulphate, and a ruthenium. Specific examples of the alkyl group include methyl group, ethyl acetate, and the like. When Z13 and Z14 are alkoxy groups which may have a substituent, the alkoxy group which may have a substituent has a carbon number of usually 1 or more, 4 or less, preferably 3 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a dentate atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include a substituent such as an oxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a ethoxy group, a 2, 3-dihydroxypropoxy group or the like. Alkoxy. Z13 and Z14 are a mercaptoamine group which may have a substituent when it may have a substituent-containing amine group, and are usually represented by -CAO, and RA represents an alkyl group which may have a substituent or a phenyl group which may have a substituent. The alkyl group has a carbon number of usually not more than the above, usually 4 or less, preferably 2 or less. The group which may be substituted on the alkyl group and the phenyl group may, for example, be an alkoxy group, a trans group, a sulfonic acid group, a carboxyl group or a γ atom. Specific examples of the mercaptoamine group include an ethenylamino group and a benzhydrylamino group. [Chem. 26]

In the formula (1 2g), Z and Z16 each independently represent a carbon number of 1 to 6 which may have a substituent. Q1 represents an oxygen atom or a sulfur atom. . 2 indicates oxygen source 312XP / invention specification (supplement) / 96-11/96119266 200815533 sub or NH base. A specific example in which the above-mentioned fields Z and z are alkyl groups which may have a substituent, and the alkyl group of 盥 Z is the same. Among the formula (1 -2-1)} and the plant pigment (12), an azo dye is preferably used for the anisotropic dye film represented by the following formula (1 2 1) in the form of a free acid. [化27]

(1) 1 &lt;A31 and A32> A31 and A32 are synonymous with the formula (1-2). &lt;R31 to R34&gt; RR independently represent a hydrogen atom, a trans group, a carboxylic acid group, a carboxyl group, and may have a substitution. The alkyl group or the alkoxy group which may have a substituent. The alkyl group which may have such a substituent is usually an alkyl group having a carbon number of i or more, 4 or less, preferably 3 or less. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group, and a carboxyl group. Specific examples of the alkyl group include a mercapto group and an ethyl group. The alkoxy group having the substituent may be mentioned. The alkoxy group having a carbon number of usually 丨 or more and 4 or less, preferably 3 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a dentate atom or a sulfonic acid group. And a carboxyl group 312XP / invention specification (supplement) / 96-11/96119266 44 200815533, etc. Specific examples of the alkoxy group include a decyloxy group, an ethoxy group, a positive group, a n-butoxy group, and a hydroxy group An alkoxy group which may have a substituent such as an oxy group, a 2, 3-dihydroxypropoxy group, etc. ~ {molecular weight} The molecular weight of the pigment (1-2), calculated as the free acid form Preferably, it is preferably 13 Å or less, and more preferably 1100 or less. [A azo dye for an anisotropic dye film of a free acid form is represented by the formula (1-3)] The above dye (1) is preferably the following The formula (Bu 3) indicates a free acid form. In the following, the azo dye for a tropic pigment film is referred to as "pigment (b 3)" by the following formula (b). 28]

{A41 and A42} A41 and Λ42 each independently represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent. The substituent may be a hydrophilic group such as a sulfonic acid group, a carboxyl group or a trans group or a group represented by the following formula (1-3a). The phenyl or naphthyl group of A or A has a bathing property with respect to water due to its hydrophilic group, and thus it is possible to suppress random association between molecules. Among them, a sulfonic acid group is preferred in terms of solubility in a solvent. [Chem. 29] 312XP / invention specification (supplement) grasping 61192 sinking 45 200815533 — N=N—D1 (i-3a) In the formula (l-3a), D1 represents a phenyl group which may have a substituent or may have a substitution Naphthyl. The side substituent may, for example, be an acid group, a thiol group, a thiol group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an amine group which may have a substituent; preferably a sulfonic acid group. An alkyl group which may have such a substituent is an alkyl group having usually 1 or more, 4 or less, preferably 3 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, an im group atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkyl group include a mercapto group and an ethyl group. The alkoxy group which may have a substituent usually has 1 or more and 4 or less, preferably 3 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a sulfonyl group, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group, a 2,3-dihydroxypropoxy group, etc., which may have a substituent. The alkoxy group is preferably a lower alkoxy group which may have a substituent. The amine group which may have a substituent is usually represented by -NH2, -NHRb, -NRCRD, and RB to RD each independently represent an alkyl group which may have a substituent or a phenyl group which may have a substituent. The number of carbon atoms of the alkyl group is usually 〗 or more, usually 4 or less, preferably 2 or less. The group which may be substituted on the alkyl group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a functional atom. Specific examples of the amine group include a methylamino group, an ethylamine group, a propylamine 312XP/invention specification (supplement)/96·〗 1/96119266 46 200815533, a dimethylamino group, a phenylamino group and the like. D1 may have one or two or more such substituents. The phenyl or naphthyl group of A41 and A42, and the molecular linearity 2 (1) is obtained to obtain an effect close to the direction. The long axis of the knife and the main absorption axis of the pigment

Furthermore, when there are a plurality of D1s in the molecule, the plurals may be the same or different. J 另 另 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J From the point of view of easiness, it is better to be the same. {X42} represents -CH2- group or -C0-group r42 {R41 to R44} R41 to R44 each independently represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, a calcinyl group which may have a substituent, a filament which may have a substituent I, The amino group or the acid group amine group 0 is an alkyl group which may have a substituent of R41 to R44, and the carbon number thereof is usually 1 or more and 6 or less, preferably 3 or less. Examples of the group which can be substituted on the alkyl group include an alkoxy group, a thiol group, a halogen atom, a rhein group, and a carboxyl group. Specific examples of the alkyl group include a methyl group and an ethyl group, and particularly preferably a lower alkyl group which may have a substituent. The alkoxy group which may have a substituent of R41 to R44 has a carbon number of usually 1 or more and 6 or less, preferably 3 or less. It can be carried out on the alkoxy group. 312XP/Invention Manual (Supplement)/96·11/96119266 47 200815533 The base of the formula can be exemplified by: alkoxy group, rhodium group, _ atom, acid group and rebellion. Base. Specific examples of the alkoxy group include an alkyl group which may have a substituent such as a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group or a 2,3-dihydroxypropoxy group. The oxy group is particularly preferably a lower alkoxy group which may have a substituent. The mercaptoamine group of R41 to R44 is represented by -nhc〇rE, and rE represents an alkyl group which may have a substituent or a phenyl group which may have a substituent. The number of carbon atoms of the alkyl group is usually 1 or more, usually 4 or less, preferably 2 or less. The group which may be substituted on the alkyl group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. Specific examples of the mercaptoamine group include an ethenylamino group and a benzoinylamino group. R41 to R44 are particularly preferably a hydrogen atom or a methyl group in terms of molecular linearity. {Y2 and Y3} Y and Y3 each independently represent a hydrogen atom, a methyl group or an ethyl group. In the C-form (1-3), the anisotropic dye film represented by the following formula (1 - 3 - 1) in the form of a free acid is preferably an azo dye. [化30]

&lt;A41, A42, X42, YH&gt; a The above formula (Bu 3) is synonymous. 48 312ΧΡ/Invention Manual (Supplement)/96-11/96119266 200815533 &lt;R45 and R46&gt; R45 and R45 and R46, which may be the same as or different from r41 to r44 R46 in the above formula (1-3), are synthesized. Rong: Sexual rumors, the same is better. In the case of the free acid form of the dye of the formula (U-3-1), the free acid form is an anisotropic pigment film represented by the following formula (&quot;-2). Even better. plant,

[化31] R47 p4$ Y2

In the formula (1-3-2), X42, Y2 and γ3 are synonymous with the above formula (1-3). R45 and R46 are synonymous with R41 to R44 in the above formula (1-3). R47 and R48 each independently represent a sulfonic acid group, a carboxyl group or a hydroxyl group. {Molecular weight} The molecular weight of the dye (1-3) is preferably ι 8 Torr or less, more preferably 1,500 or less, in terms of the free acid form. [Azo dye for an anisotropic dye film of a free acid form in the formula (1-4)] The above dye (1) is preferably represented by the following formula (1-4) in the form of a free acid. In the following, the azo dye used for the anisotropic dye film of the free acid form is represented by the following formula (Bu 4) as "pigment (1 - 4)". 312ΧΡ/Invention Manual (supplement)/96-11/96119266 49 200815533 [Chem. 32]

{A51 and A52} 51 A and A each independently represent a phenyl group which may have a substituent or a group which may have a substituent. A and A may be the same or different, but the same is preferred. When A or A 2 is a naphthyl group, the azo group bonded to the 2-position of the naphthalene ring may be a substituent which may be possessed on the phenyl or naphthyl group of the preferred 0 A51 and A52, and examples thereof include a sulfonyl group. And a carboxyl group, an amine carbenyl group which may have a substituent, an amine sulfonyl group which may have a substituent, a salt which may have a substituent, an alkoxy group which may have a substituent, and an amine group which may have a substituent. The group which may be substituted on the amine mercapto group which may have a substituent may, for example, be an alkyl group having a carbon number of 丨4. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the amine onylide group which may have a substituent include an amine methyl group and an N-methylamine methyl group. The group which may be substituted on the aminesulfonyl group which may have a substituent may, for example, be a carbon group which may be substituted. The base which can be substituted on the city base is exemplified by an alkoxy group, a hydroxyl group, a (tetra) atom, a sulfonic acid group, and a carboxy group 312XP/invention specification (supplement)/9641/961192, 50 200815533, and the like. Specific examples of the aminesulfonyl group which may have a substituent include an aminesulfonyl group and an N-decylamine group. The alkyl group which may have such a substituent is usually an alkyl group having a carbon number of not less than 丨, not more than 6 and preferably not more. Examples of the group to be substituted on the alkyl group include a decyloxy group, a hydroxyl group, a halogen atom, a sulfonic acid group, and a carboxyl group. Specific examples of the alkyl group include a mercapto group, an ethyl group and the like, and particularly preferably a lower alkyl group. The alkoxy group which may have such a substituent is usually a carbon number! Above or below 4, preferably 3 or less alkoxy groups. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include an alkoxy group which may have a substituent such as a decyloxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group or a 2,3-dihydroxypropoxy group. The group is particularly preferably a lower alkoxy group which may have a substituent. The amine group which may have such a substituent is usually represented by -2, -NHRF, #-WRY, -NHCOR1, and f~R1 each independently represents a phenyl group which may have a substituent or a phenyl group which may have a substituent. The number of carbon atoms in the base is usually 1 or less, usually 4 or less, preferably 2 or less. The group which may be substituted on the phenyl group and the phenyl group may, for example, be an alkoxy group, a thiol group, a rhein group, a carboxyl group or a halogen atom. Specific examples of the amine group include a methylamino group, an ethylamino group, a propylamino group, a dimethylamino group, a phenylamino group, an ethylamino group, and a benzhydrylamino group. The substituent of ^ and ^, wherein a sulfonic acid group, a few groups, and a hydroxyl group are preferred. A and A may each have one such substituent, and may have two substituents of 312XP/invention specification (supplement)/96-11/96Π9266 c, 200815533 or above. {R51 and R52} R and R52 each independently represent a hydrogen atom, a trans group, a halogen atom, a repeating acid group, a carboxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent or an amine group which may have a substituent . Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. The base which may have such a substituent is a burnt group having a carbon number of usually 1 or more and 4 or less and a carwort of preferably 3 or less. The group which may be substituted in the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkyl group include a mercapto group and an ethyl group. The alkoxy group which may have such a substituent is an alkoxy group having a carbon number of hereinafter or more, 4 or less, preferably 3 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a stilbene atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group, a 2,3-dihydroxypropoxy group, etc., which may have a substituted ruthyl group. Alkoxy. The amine group which may have such a substituent is usually represented by -, -NHR j, -nrKrL, -NHCORM, and -Rm each independently represents a thiol group which may have a substituent or a phenyl group which may have a substituent. The alkyl group is an alkyl group having a carbon number of usually i or more, usually 4 or less, preferably 2 or less. The group which may be substituted on the alkyl group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. Specific examples of the amine group include a methylamino group, an ethylamino group, a propylamino group, a diammonium group, a phenylamino group, an ethylamino group, and a benzylamino group. 312XP/Invention Manual (supplement)/96-11/96119266 52 200815533 R and R52, only 丨丨 士 声 声 乙 乙 “ “ 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以Ethyl group, stone to buy acid group, and when it is substituted for its position in benzene: soil:, when there are multiples taken, {molecular weight 丨 is not adjacent to the carbon atom in the clothing position. 1 4) Knife summer, in the form of free acid, preferably less than 1 500, more preferably less than 1200. Bu Ma [2] implementation form 2 [Λ Λ (2) table ί free acid form anisotropy The monoazo dye for the pigment film is a monoazo dye for the anisotropic pigment film of the second aspect, and the free acid form is represented by the following formula (2). Hereinafter, the following will be used as the free acid. The form of the anisotropic pigment film monomonoazo pigment is called a pigment (2). [化33]

(2) In the formula (2), Α3 represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a group represented by the following formula (1-10,000). X7 represents a -CH2- group or a -CO- group. Γ6 represents an indole, a thiol or an ethyl group. R13 to R15 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, may have a substituent 312ΧΡ/invention specification (supplement)/96-11/96119266 53 200815533 ^Amine group, Sulfonic acid group, hydroxyl group, nitro group or carboxyl group. AP represents 丨, and the base is 1' 4 , N, N, 1,5-naphthyl, 2,6-anthranyl or the group represented by the following formula (1-a2).丨, 4-phenylene, 14-anthranyl, 15-naphthyl, 2,6-anthranyl, and a group represented by the following formula (1_a2) may have a substituent. [34]

(1) In the formula y-ys), Q13 and Q each independently represent an oxygen atom or a group. R and R94 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amine group which may have a substituent. It can be combined with R94 to form a ring.

In the formula (l-a2), the ring stone is a heterocyclic ring of 5 or 6 membered rings. {A3} <Phenyl group> When A is a phenyl group which may have a substituent, the phenyl group may have a substituent, and examples thereof include a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group, and an alkoxy group which may have a substituent. Amino group which may have a substituent, an alkyl group which may have a substituent, 312XP/Invention specification (supplement)/96-11/96119266 54 200815533 Alkenyl group which may have a substituent, amine amidoxime which may have a substituent A group, an aminesulfonyl group which may have a substituent, a phenyl group which may have a substituent, an aryloxy group which may have a substituent, and the like. The alkoxy group as a substituent has a carbon number of usually 1 or more, usually 6 or less, preferably 4 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group, a 2,3-dihydroxypropoxy group, etc., which may have a substituent. The alkoxy group is particularly preferably a lower alkoxy group which may have a substituent. The amine group as a substituent is usually represented by -NHR111 and -NR112R113. R111 to R113 each independently represent an alkyl group which may have a substituent, a phenyl group which may have a substituent or an indenyl group which may have a substituent. The number of carbon atoms of the alkyl group is usually 1 or more, usually 12 or less, preferably 1 or less. The fluorene group is represented by -C0R114, and R114 represents an alkyl group which may have a substituent, a emulsifiable group which may have a substituent, a dilute group which may have a substituent, or a phenyl group which may have a substituted ruthenyl group. The number of carbon atoms of the alkyl group and the alkoxy group is usually 1 or more, usually 6 or less, preferably 4 or less, and the number of carbon atoms of the alkenyl group is usually 1 or more, usually 12 or less, preferably 1 Å. the following. Examples of the group which may be substituted on the alkyl group, the alkoxy group, the alkenyl group and the phenyl group include an alkoxy group, a thiol group, a sulfonic acid group, a fluorenyl group, and a halogen atom. The group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group of R111 to R113 may, for example, be a phenyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom which may have a substituent. The group which can be substituted on the phenyl group may, for example, be a sulfonic acid group, a carboxyl group or a hydroxyl group. 312XP/Invention Manual (Supplement)/96·11/96119266 55 200815533 * Specific examples of the amine group include an amine group, a methylamino group, an ethylamine group, a 2-amino group, a 4-1⁄2 group. A strepylamino group, a 4-carboxyphenylmercaptoamine group, a fumartenylamino group, and the like. The alkyl group as a substituent has a carbon number of usually 丨 or more, usually 6 or less, preferably 4 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. The alkyl group may, for example, be a methyl group or an ethyl group, and particularly preferably a lower alkyl group which may have a substituent. The alkenyl group which is a substituent has a carbon number of usually i or more, usually U or less, preferably 1 Å or less. The group which may be substituted on the alkenyl group may, for example, be an alkyl group, a phenyl group or a carboxyl group. Specific examples of the alkenyl group include a trans-2-carboxyvinyl group and a trans-2-(2-sulfophenyl)vinyl group. The amine carbenyl group as a substituent has a carbon number of usually i or more, usually 6 or less, preferably 4 or less. The group which can be carried out on the amine mercapto group may, for example, be an alkyl group having 1 to 4 carbon atoms which may be substituted. Specific examples of the amine methyl sulfhydryl group which may have a substituent include an amine fluorenyl group and an N-methylamino fluorenyl group. The amine hydrazide group as a substituent has a carbon number of usually 1 or more, usually 6 or less, preferably 4 or less. The group which can be substituted on the aminesulfonyl group may be a calcined group having 1 to 4 carbon atoms which may be substituted. Specific examples of the amine κ I group which may have a substituent include an amine yellow wine base and an n-methyl amine ruthenium base group. The phenyl group as a substituent has a carbon number of usually 6 or more, usually 1 Å or less, preferably 8 or less. The group which may be substituted on the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group or a carboxyl group. Specific examples thereof include a phenyl group which may have a substituent such as a phenyl group, a 3-sulfophenyl group or a 4-sulfophenyl group. 312XP/Invention Manual (Supplement)/96·11/96119266 56 200815533 The aryl group constituting the aryloxy group as a substituent is preferably a phenyl group or a naphthyl group; and the aryl group may have a substituent, and an alkane may be mentioned. Alkyl group, alkoxy group, carboxyl group, sulfonic acid group, hydroxyl group and the like. Specific examples of the aryloxy group which may have a substituent include a phenoxy group, a 2-naphthyloxy group, a p-methylphenoxy group, a p-methoxyphenoxy group, an o-carboxyphenoxy group and the like. When the phenyl group of A3 has a substituent, it is preferred to carry out the treatment with a hydrophilic group such as a sulfonic acid group, a carboxyl group or a hydroxyl group from the viewpoint of solubility in water. Further, from the viewpoint of color tone, the number of substitutions of the amine group or the hydroxyl group which may have a substituent is preferably 2 or less. The phenyl group may have one or more such substituents, and may have two or more such substituents, but the substituent is preferably three or less. The substitution position of the substituent is substituted in the meta or para position with respect to the azo group, and is preferable because the molecular linearity is high. <Naphthyl group> 0 When A3 is a naphthyl group which may have a substituent, the naphthyl group may have a substituent, and examples thereof include a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group, an alkoxy group which may have a substituent, Amine group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an amine fluorenyl group which may have a substituent, an amine sulfonyl group which may have a substituent, a benzene which may have a substituent A group, an aryloxy group which may have a substituent, and the like. Specific examples of the substituent of the naphthyl group When A3 is a phenyl group, specific examples of the substituent of the phenyl group are the same as those described above. When the naphthyl group has a substituent, from the viewpoint of solubility in water, 312XP/invention specification (supplement)/96-11/96119266 57 200815533 is preferably a hydrophilic group such as a (tetra) group, a carboxyl group, a trans group or the like. Substituting for sex. Further, from the viewpoint of y, the number of substitutions of the amine group or the base group which may have a substituent is preferably one or less. A naphthyl group which may have a substituent, which may have! Further, the substituent may have two or more such substituents, but the substituent is preferably 4 or less, more preferably 2 or less. In the case of sub-J: linearity, t is preferable to the azo group to avoid the naphthyl group, and the other substituents are substituted at the station, 4, 5, 4 or 7 positions. The replacement is better. On the other hand, from the viewpoint of color tone, azo is in the opposite to the naphthyl group! Substitution is preferably carried out at the position, and other substituents are preferably substituted at the 1, 4 or 5 positions. <Aromatic heterocyclic group> A. An aromatic heterocyclic group which may have a substituent, preferably a group derived from a monocyclic or bicyclic heterocyclic ring. The atom other than carbon constituting the aromatic heterocyclic group may, for example, be an atom, a sulfur atom or an oxygen atom. When the aromatic heterocyclic group has a plurality of atoms constituting the ring other than the stone, these may be the same or different. The aroma: a heterocyclic group is preferably an aromatic heterogeneous carbon having a carbon number of 3 or more and 1 or less. Although a polycyclic aromatic heterocyclic ring is used, the heterocyclic moiety may be bonded to an azo group, and the hydrocarbon ring moiety may be Combined with an azo group. Specific examples of the aromatic heterocyclic group include a pyridyl group, a quinolyl group, a thiopyranyl group, a thiol group, a benzofluorenyl group, a quinone ketone group, a decyl group of naphthoic acid, and a ruthenium group. Base, π is an oxime group, and the like. When the "heterocyclic group which may have a substituent group", the substituent of the substituent group may, for example, be an alkoxy group, a aryl group, a nitro group, an alkoxy group which may have a substituent, or an amine which may have a substituent The group may have a substituent 312ΧΡ/invention specification (supplement)/96-11/96119266 58 200815533; an alkenyl group which may have a substituent, an amine mercapto group which may have a substituent, may have a substituent a sulfonyl group, a phenyl group which may have a substituent, a cyano group, etc. Specific examples of the substituent of the 5-membered aromatic heterocyclic group, when A3 is a phenyl group, a specific example of the substituent of the phenyl group, and the foregoing When the aromatic heterocyclic group of A3 has a substituent, it is substituted with a hydrophilic group such as a sulfonic acid group, a carboxyl group or a hydroxyl group, which is preferable from the viewpoint of solubility in water. In view of the above, the number of substitutions of the amine group or the hydroxy group which may have a substituent is preferably two or less. The aromatic heterocyclic group which may have a substituent may have one or more of these substituents, and may have Two or more of these substituents, but the substituent is preferably 4 or less, more preferably 2 or less. 1- / 3) represents the group> A in the above formula may also be (1 - no) of the group represented by [Formula 36].

In the formula (Bu), Q13 and Q14 are independent of each other, XL VIII, and v, 丄 _ and R94 respectively represent a hydrogen atom, ί stands for an oxygen atom or an NH group. An alkyl group which may have a substituent or an amine group which may have a substituent. R93 and r94 may also combine to form a ring.

312 ΧΡ / Invention Manual (Supplement) / 96-11/96119266 59 200815533 The group to be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a dentate atom, a sulphate group or a carboxyl group. Specific examples of the alkyl group include a mercapto group, an ethyl group and the like, and particularly preferably a lower alkyl group which may have a substituent. The amine group of R and R94 which may have a substituent, and is usually represented by - leg 2, -NHRm, -NR R . The alkyl group which may have a substituent, the phenyl group which may have a substituent, or the fluorenyl group which may have a substituent are each independently represented. The number of carbon atoms of the alkyl group is usually 丨 or more, usually 12 or less, preferably 10 or less. The fluorenyl group is represented by -c〇R218, and R218 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent. The carbon number of the alkyl group and the alkoxy group is usually 1 or more, usually 6 or less, preferably 4 or less. The δ inverse is usually 1 or more, usually 12 or less, and more preferably 10 or less. The group which may be substituted on the alkyl group, the alkoxy group, the alkenyl group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. The group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group of R to R may, for example, be a phenyl group, an alkyl group, an alkoxy group, a mercaptoamine group, a hydroxyl group or a sulfonic acid group which may have a substituent. Carboxyl group, halogen atom, and the like. The phenyl group may have a substituent group, and examples thereof include a sulfonic acid group, a carboxyl group, and a hydroxyl group. Further, when m η is combined to form a ring, a group having a carbon group, a thiol group or the like can be used as a substituent of the amine group. The group represented by the formula (1-厶) has a carbon number of preferably 3 or more and 12 or less, and specific examples thereof include the following. 312ΧΡ/Invention Manual (Repair)/96·1ι/96ιΐ9266 60 200815533 [Chem. 37]

Vch3 CH

&gt;-nh —GH /=S }^m 0

Preferred Example of SO3H &lt; A3> As A, a phenyl group which may have a substituent or a naphthyl group which may have a substituent is preferable. The substituent is preferably a sulfonic acid group, a carboxyl group or an alkoxy group which may have a substituent, and it is preferred to have one or two such groups as a substituent. {X7} X7 represents a -CH2- group or a -C0- group. {Y6} γ represents a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group. {R13 to R15} R R is independently an alkyl group which may have a substituent, an alkyl group which may have a substituent, an amine group which may have a substituent, an amine group which may have a substituent, a nitro group, a tartaric acid group, a hydroxyl group or a carboxyl group. The alkyl group of R to R has a carbon number of usually 1 or more, usually 4 or less, preferably 3 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a sulfonic acid atom, a sulfonic acid group or the like. The base of the alkyl group may be a methyl group, an ethyl group or the like, and particularly preferably a lower alkyl group which may have a substituent. 61 200815533 The alkoxy group of R13 to R15 has a carbon number of usually i or more, usually 4 or less, preferably 3 or less. Examples of the substituent which may be substituted on the alkoxy group include an alkoxy group, a sulfonium atom, and a water/grain group such as a thiol group, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group, and a 2,3-dihydroxypropoxy group. The alkoxy group, particularly the lower alkoxy group which may have a substituent, is preferably an amine group of R13 to R15, and is usually shown by -NH2, -NHRn, -NRPRQ. Rn to rq each independently represent an alkyl group which may have a substituent, a phenyl group which may have a substituent or a mercapto group which may have a substituent. The carbon number of the alkyl group is usually 1 or more, usually 12 or less, preferably 10 or less. The fluorenyl group is represented by -C0RR, and Rr represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent. The carbon number of the alkyl group and the alkoxy group is usually _ or more, usually 6 or less, preferably 4 or less. The number of carbon atoms of the alkenyl group is usually 1 or more, usually 12 or less, preferably 1 or less. The group which may be substituted with the alkyl group, the alkoxy group, the alkenyl group and the phenyl group may, for example, be an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom. The group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group of RN to RQ may, for example, be a strepyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group or a halogen atom which may have a substituent. The group which may have a substituent on the phenyl group may, for example, be a sulfonic acid group, a carboxyl group or a hydroxyl group. Specific examples of the amine group include an amine group, a methylamino group, a dimethylamino group, and a 312XP/invention specification (supplement)/96-11/96119266 62 200815533 $based 2_stone group ethylamine group, 4-sulfophenylamino group, 4-carboxybenzhydrylamino group, anti-butylene decylamino group, and the like. |Γ) 1 3 iTN | 5 ^ 〃~' From the viewpoint of solubility in water, interaction with substrate, or durability, it has hydrogen atom, hydroxyl group, sulfonic acid group, carboxyl group, sulfhydryl group, and An alkoxy group having a water-soluble group such as an oxy group, an ethoxy group, a 2, 3-dihydroxypropoxy group, an amine group, a decylamino group, or a thio group as a substituent, or a substituent having the water-soluble group as a substituent Amine groups are preferred. <Preferred Example of R and R 4 _ R &amp; R14, each independently being a hydrogen atom, a thio group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, a sulfonic acid A base or a hydroxyl group is preferred. lAr21} Red 21 represents i,4-phenylene, [,4_anthranyl, anthracene, 5-naphthyl, 2,6-naphthyl or a group represented by the following formula (i-a2), Preferably, it is an L4-phenylene group, a 1,4-naphthyl group, more preferably an anthracene, and a 4-phenylene group. 〖, 4-phenylene, anthracene, 4-terinylnaphthyl, 1,5-anthranyl, 2,6-anthranyl, and a group represented by the following formula (l-a2), may have a substituent . [化38]

(1. In the formula (1-a2), the ring stone is a heterocyclic ring of 5 or 6 membered rings. % is combined with a benzene ring in the formula (1 - a 2 ) to form a condensed ring. 312XP/Invention Manual (Supplement) /%_ 11/96119266 63 200815533

The condensed ring group can be exemplified by 喹 ψ · A , , + k . quinoline diindolyl, isoquinolinyl dihydrazino, benzene out: as in the formula (1- must be shown in the Λ罟Γ Λ罟Γ, The oxime position is located at a position opposite to each other in the benzene ring portion. The 1-2 has the following substituents: each may independently have a substitution ε, an alkoxy group having a substituent, and may have a substituent. Amine earth &amp; earth atom, rhein acid group or warp group. In terms of molecular linearity or solubility to water, α2Ι ^ ^ , 〇σ Af has no substituent, or has methyl group, methoxy group, It is preferred that the 2,3-di-carbyl group is a gas, and /&gt; ^ ^ ^ is a propyl group, a fluorenyl group, a sulphate group or an ethylamino group as a substituent.

Ar may have one such substituent, and may have two or more such substituents. However, the substituent is preferably three or less, more preferably two or less. When there are two or more such substituents other than a hydrogen atom, the substituent is preferably substituted with 0 φ or less at the adjacent atom of the ring from the viewpoint of molecular directness and dimorphism, and Αι*21 Specific examples of substituents that may be present. The number of carbon atoms of the alkyl group is usually i or more, usually 6 or less, preferably 4 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a repeating acid group or a secret group. Specific examples of the alkyl group include an amino mercaptoethyl group, and particularly preferably a lower alkyl group which may have a substituent. The inverse number of the alkoxylate is usually 1 or more, usually 6 or less, preferably 4 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethyl group 312XP/invention specification (supplement)/9641/96119266 64 200815533 oxy group, 2, The alkoxy group which may have a substituent such as 3-dimethoxypropoxy group, and the like, particularly preferably a lower alkoxy group which may have a substituent. The amine group is usually represented by - leg 2, -NHIT 1, -NWi, and Ra] to Rrl each independently represent an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a fluorenyl group which may have a substituent. The number of carbon atoms of the alkyl group is usually 丨 or more, usually 4 or less, preferably 2 or less. The fluorenyl group is represented by —c〇R”, and R51 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a phenyl group which may have a substituent. The alkyl group and the alkoxy group thereof The number of carbon atoms is 1 or more, usually 4 or less, preferably 2 or less. The group which can be substituted on the alkyl group, the alkoxy group and the phenyl group may, for example, be an alkoxy group. And a group which may be substituted on the alkyl group, the phenyl group or the fluorenyl group, and examples thereof include an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, and a functional group. Atom atom, etc. Specific examples of the amine group include an amine group, a guanylamino group, an ethylamino group, a propylamino group, an amino group, a phenylamino group, an acetamino group, and a benzoguanamine. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom {molecular weight} The molecular weight of the dye (2), preferably 15 Å or less in terms of the free acid form, and 1200 or less. More preferably. [Formula (2-1) shows an azo dye for an anisotropic dye film in a free acid form] The above dye (2) is in the form of a free acid In the following, the monoazo dye used for the anisotropic dye film of the free acid form is represented by the following formula (2-1) as "pigment (2 - υ". 312 ΧΡ / invention specification ( Supplement)/96-11/96119266 65 200815533 [Chem. 39] R63 A63

R65

(24) {A63} Benzene as a substituent for 63 days, no i or 2 groups selected from the group consisting of a mineral acid group, a carboxyl group and a group of alkoxy groups which may have a substituent 2 alkoxy group Base or niche. When the phenyl group and the naphthyl group have a plurality of substituents, the substituents may be the same or different. / The substituent having an alkoxy group of the substituent may, for example, be a trans group, a thiol group or a f acid group. Further, the alkoxy group is preferably a methoxy group having 1 to 4 carbon atoms. The base group or the naphthyl group may have a substituent in the case of the substituted ruthenium group other than the above-mentioned substituent, and may be exemplified as a phenyl group or a naphthalene when A3 in the above formula (2) is a phenyl group or a phenyl group. The substituents may be exemplified by the substituents. When the phenyl group of the genus has a substituent, it is bonded to the azo group at the 3-position or the 4-position, and is preferred because it has high molecular linearity. Further, when Aw is a naphthalene, the azo group is bonded to the 2-position of the naphthalene ring of the naphthalene group, and when it has a substituent, it is 5, 6 or 7 It is preferred to have a substituent on the site. {R63 and V4} κ and π each independently represent a hydrogen atom, a substituent which may have a substituent, 312ΧΡ/invention specification (supplement)/96-11/96119266 66 200815533 alkoxy group which may have a substituent, may have a substitution Amino group, sulfonic acid group or a trans-group. The carbon number of the burnt group is usually 1 or more, usually 4 or less, preferably 3 or less. The group which may be substituted on the alkyl group may, for example, be an alkoxy group, a hydroxyl group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkyl group include an amine group, a mercapto group, and an ethyl group, and particularly preferably a lower alkyl group which may have a substituent. The number of carbon atoms of the alkoxy group is usually 1 or more, usually 4 or less, preferably 3 or less. The group which may be substituted on the alkoxy group may, for example, be an alkoxy group, a ruthenium group, a halogen atom, a sulfonic acid group or a carboxyl group. Specific examples of the alkoxy group include an alkyl group which may have a substituent such as a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a hydroxyethoxy group or a 2,3-dihydroxypropoxy group. The oxy group is particularly preferably a lower alkoxy group which may have a substituent. Specific examples of the amine group which may have a substituent are the same as those described for the substituent of red £1 in the formula (2). In terms of molecular linearity or solubility in water, it is preferred that R63 and the reference are independently a halogen atom, a methyl group, a methoxy group, a 2,3-dihydroxypropoxy group, a sulfonic acid group or an ethyl hydrazine. Amino group. {R65 and R66} R65 and R66 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, a carboxyl group or a repeating acid group. Specific examples of the alkyl group which may have a substituent, the alkoxy group which may have a substituent, and the amine group which may have a substituent are the same as those described as a specific example of r13 to r1S in the formula (2). 312XP/Inventive Manual (Supplement)/96-11/96119266 67 200815533=In terms of linearity or solubility in water, it is preferred that r65 and propyl sulfonate I are ruthenium atoms, methyl groups, methoxy groups, Ethoxy, 2,3-di-{R67} R represents a hydrogen atom, a nitro group, a silk group which may have a substituent, a trans group or an amine group which may have a substituent. The alkoxy group which may have a substituent, the amine group which may have a substituent, and the specific examples of γ to f in the formula (2) are the same. R is a k-oxy group having a water-soluble group such as a hydroxyl group, a sulfonic acid group or a carboxyl group as a substituent in terms of solubility in water, interaction with a substrate, or durability, and has the water-soluble group as a substituent. The substituted amino group, benzhydryl mercaptoamine group, amine group, methylamino group, diammonium group, and hydroxyl group are preferred. {Molecular weight} The molecular weight of the dye (2-1) is preferably 15 Å or less, more preferably 1200 or less, in terms of the free acid form. _ [Mono azochrome for an anisotropic dye film of a free acid form in the formula (2-2)] The above dye (2) is preferably represented by the following formula (2-2) in the form of a free acid. In the following, the monoazo dye used for the anisotropic dye film of the free acid form is represented by the following formula (2-2) as "pigment (2-2)". 312XP/Invention Manual (supplement)/96-Π/96119266 68 200815533 [化40]

Ref.-2" {A73} 2 is a phenyl group which may not have a substituent or a naphthyl group which may have a substituent. The "X-substituent group" includes a hydrophilic group such as a sulfonic acid group, an aryl group or a thiol group. The base group or the naphthyl gene has a hydrophilic group and thus has solubility in water, thereby suppressing random association between molecules. The solvent is preferably a sulfonic acid group. A ' may have one or more hydrophilic groups, and may have two or more hydrophilic groups. {X7} X7 represents -CH2 -Base or -(3)-Base. {Y6} Y6 represents a hydrogen atom, a methyl group or an ethyl group. {R73 and R74} R73 and R74 each independently represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, an alkyl group which may have a substituent, An alkoxy group, an amine group or a mercaptoamine group which may have a substituent. A specific example of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, and In the case of the substituent of Arn, the same is true. 312XP/Invention Manual (Supplement)/96-11/96119266 69 200815533 In terms of molecular linearity, it is preferred that R73 and R74 are each independently a gas atom or a ruthenium. When R73 and R74 have two or more substituents other than a hydrogen atom, the substituent is in the ring The substitution is preferably carried out at the adjacent atom. {Molecular weight} The molecular weight of the dye (2-2) is preferably 1,500 or less in terms of the free acid form, more preferably 1 200 or less. {Formula (2-2-1)} In the above-mentioned dye (2-2), a monoazo dye is used for the anisotropic dye film represented by the following formula (2-2-1) in the form of a free acid. [Chem. 41]

(2 Winter 1) In the formula (2 - 2-1), An, r, and χ7 are synonymous with those in the formula (2-2). R76 is synonymous with R73 or R74 in the formula (2-2). The molecular weight of the dye of the free acid form is represented by the formula (2-2-1), and it is preferably 1,500 or less in terms of the free acid form, more preferably 12 Å or less. The pigment of the present invention generally has high dichroism in a short-wavelength region, but in the use of high-blue light color purity, it is preferable to have a dichroic property in a restricted range. . Moreover, in order to be used in combination with a conventional dichroic substance, it is preferred to display high dichroism in an insufficient wavelength range only in the conventional 312XP/#Hg^^(^)/96^1/96119266 70 200815533 material. It is preferred that the absorption half-value of the pigment is narrow and narrow. That is, among the dyes of the present invention, monoazo dyes are particularly preferred. Here, the term "monoazo dye" as used in the present invention means a dye in which a plurality of azo groups are conjugated via 7 而非 instead of being linked. In the present invention, a single azo dye can be obtained by cutting a total of two azo groups in the i molecule. [3] Salt type The azo dyes (1) and (2) which are azo dyes for anisotropic pigment films of the present invention are usually water-soluble dyes. μ The azo dye used for the anisotropic dye film of the present invention can be used as it is as a free acid (free acid form), or a part based on an acid group can be a salt type. Further, the salt type pigment may be mixed with the free acid type pigment. When it is obtained in the form of a salt, it can be used directly or in the form of a desired salt type. As a salt type exchange method, the following methods can be used. For example, 1) an aqueous solution of a pigment obtained by adding a salt to an aqueous dye solution obtained by a salt type, and performing acid precipitation after a free acid form, and neutralizing the acidic base type with a desired pair of neutralization In addition, a method of adding a neutral salt having a desired counter ion (for example, a method of salt exchange of chlorine in a separate form, a reduction in salt, a salting-out filter, and a shape of a cake 3) is carried out to treat the color of the octyl ester obtained in a salt form. After the pigment is exchanged in a free: liquid cation exchange tree, the acidity of the pigment is introduced into the (four) liquid (for example, an aqueous solution of sodium hydroxide solution) having 312^mmmmmm/96Ai/96U9266 71 200815533 (4). And water exchange with salt 4) The aqueous solution of the pigment obtained in the salt form is exchanged with a strong acid cation exchanged with an ion-containing test solution (for example, a hydrogen storage solution or a hydrogen peroxide). Role Salt deposit and 'the present invention enable anisotropic dye azo dye system becomes a free acid type or salt type, become out of soil

PH value. Therefore, the coffee and pigment solution of the pigments described herein have two or more of the divalent groups of the anisotropic pigment film, which are the free acid type, the salt type and the acidic group. a mixture of a free acid form and a salt form, or a salt of two or more types, a sulphuric acid of an azo dye in a directional pigment film, and a composition for an anisotropic dye film. The effect of the treatment in the solution containing the dissociable salt of the substrate containing the pigment for the pigment for anisotropic pigment film is preferably the same as that of the step towel for producing the anisotropic pigment film. The above-mentioned example of the isolated 5L can be exemplified by a metal salt such as Na, L or κ, which can be substituted with a salt or a silk, or a salt of an organic amine. Examples of the organic amine include a low (tetra)ylamine having a carbon number of 1 to 6, a lower linear amine having a carbon number of 1 to 6 substituted by a radical, and a lower alkylamine having a carbon number of i to 6 Wait. When it is such a salt type, the type thereof is not limited to one type, and a plurality of kinds of the salt may be mixed. In addition, a plurality of salts may be mixed in one molecule of the compound, or a plurality of salts may be mixed in the composition. . 312XP / invention manual (supplement) /9641/96119266 72 200815533 type] V: anisotropic pigment film with azo pigment acid base of the preferred capacity (four), after the material &quot; Lai Cheng's internal 2 value for water When there is a high solubility, when the _ 7 ^ r shoulder has a ruthenium dye concentration, etc.), it is preferably an organic group having a lithium cation, a diethylamine salt, or a water-soluble group; one or more are preferable. Another ancient product, ^ less '/ 寻心孤甲, in the pigment system 2: "! When water has low solubility (for example), to present, r miscellaneous 1, pigment in the liquid solution to precipitate the pigment, etc. or It is preferable that one or more of the alkaline earth metal salt such as a sulfonium type, a sodium salt, a potassium salt, or a calcium salt is used. [4] Specific examples of the pigments Hereinafter, the anisotropy of the present invention is disclosed. For example, the present invention is not limited to, and the specific acid form of the I pigment is described. In 4 cases, the following specific examples are

312XP/^03 manual (supplement)/96·11/96119266 73 200815533[化42]

312XP/Invention Manual (supplement)/9641/96119266 74 200815533 [Chem. 43]

312XP/Invention Manual (supplement)/9641/96119266 75 200815533 [Chem. 44]

312XP/Invention Manual (supplement)/96-11/96119266 76 200815533 [Chem. 45]

312XP/Invention Manual (supplement)/96-11/96119266 77 200815533 [Chem. 46]

312XP/Invention Manual (supplement)/96-11/96119266 78 200815533 [Chem. 47]

312XP/Invention Manual (supplement)/96-11/96119266 79 200815533[化48]

312XP/Invention Manual (supplement)/96-11/96119266 80 200815533[化49]

312XP/Invention Manual (supplement)/96-11/96119266 81 200815533 [Chem. 50]

312XP/Invention Manual (supplement)/96-11/96119266 82 200815533 [Chem. 51]

312XP/Invention Manual (supplement)/96-11/96119266 83 200815533 [Chem. 52]

O^i

312XP/Invention Manual (supplement)/96-11/96119266 84 200815533 [Chem. 53]

312XP/Invention Manual (supplement)/96-11/96119266 85 200815533 [Chem. 54]

312XP/Invention Manual (supplement)/96-11/96119266 86 200815533 [Chem. 55]

312XP/Invention Manual (supplement)/96-11/96119266 87 200815533 [Chem. 56]

312XP/Invention Manual (supplement)/9641/96119266 88 200815533 [化57]

312XP/Invention Manual (supplement)/96-11/96119266 89 200815533 [Chem. 58]

312XP/Invention Manual (supplement)/96-11/96119266 90 200815533 [Chem. 59] u — 1 &gt;

312XP/Invention Manual (supplement)/96-11/96119266 91 200815533 [Chem. 60]

(i a 6)

312XP/Invention Manual (supplement)/96-11/96119266 92 200815533 [Chem. 61]

312XP/Invention Manual (supplement)/96-11/96119266 93 200815533 [Chem. 62]

Ur-yu

(I 1-8) HO Yu

312XP/Invention Manual (supplement)/96-11/96119266 94 200815533[化63]

312XP/Invention Manual (supplement)/96-11/96119266 95 200815533 [Chem. 64]

312XP/Invention Manual (supplement)/96-11/96119266 96 200815533 [Chem. 65]

312XP/Invention Manual (supplement)/96-11/96119266 97 200815533 [Chem. 66]

312XP/Invention Manual (supplement)/96-11/96119266 98 200815533 [Chemistry 67]

〇V^9) HO3S (IV-10) ΜΟφ 卿)

^r〇-' 0CH3

OH

Section OOHa

IrO^ •CHa

H

HQaS

kxP mn

312XP/Invention Manual (supplement)/96-11/96119266 99 200815533 [Chem. 68]

312XP/Invention Manual (supplement)/96-11/96119266 100 200815533 [Chem. 69]

312XP/Invention Manual (supplement)/96-11/96119266 101 200815533 [Chem. 70] Both 30)

HO^S (turn ho3s

OH

POOH (IV-32)

HQs&amp;

Η3°°ν ^

OH

312XP/Invention Manual (supplement)/96-11/96119266 102 200815533 [Chem. 71]

312XP/Invention Manual (supplement)/9641/96119266 103 200815533 [Chem. 72]

312XP/Invention Manual (supplement)/96-11/96119266 104 200815533 [Chem. 73]

312XP/Invention Manual (supplement)/96-11/96119266 105 200815533 [化74] _4) H〇aS—

312XP/Invention Manual (supplement)/96-11/96119266 106 200815533 [Chem. 75]

312XP/Invention Manual (supplement)/96-11/96119266 107 200815533 [Chem. 76]

Ο1 · nh2

HQaS 312XP/Invention Manual (supplement)/96-11/96119266 108 200815533 [Chem. 77]

312XP/Invention Manual (supplement)/96-11/96119266 109 200815533

312XP/Invention Manual (supplement)/96-11/96119266 110 200815533 [Chem. 79]

312XP/Invention Manual (supplement)/96-11/96119266 111 200815533 [Chem. 80]

NHCO continued

SO3H

312XP/Invention Manual (supplement)/96-11/96119266 112 200815533 [Chem. 81]

Further, specific examples of A21, A22, Ar1, and Ar2 in the dye represented by the formula (1-1) are disclosed below. These combinations can be used as the formula Ο-1). 312XP/Invention Manual (supplement)/96-11/96119266 113 200815533 [Chem. 82] A22

• Ar1 - M - X2 - Ar2 ~ N

[化83]

312XP/Invention Manual (supplement)/96-11/96119266 114 200815533 [Chem. 84]

CH3 Ό~!

NH^ H^CO HHa QCHa

OOH3

HO

312XP/Invention Manual (supplement)/96-11/96119266 115 200815533[化85]

312XP/Invention Manual (supplement)/96-11/96119266 200815533 [Chem. 86]

(At1)

OCH3

So3h

HaCO

H3G0 HsC HO3S

_ order H2N

[4] Method for synthesizing a dye No. (li)~(1-v), (2-i)~(2-ii) 117 312XP/invention specification (supplement)/96-11 /96119266 200815533 Expressed as free acid. [Synthesis of Pigment (1)] The following pigment (pigment No. (1-i)) can be produced by the following formula (Ι-i). [化88]

(1-0 曱) according to the hanging method [for example, Hiroshi Hiroshi "New Dye Chemistry" (refer to i973 日口 and 4 „月 21 g, 技报堂 issued), page 396, 4〇9, anti-3 amino benzene &amp; The acid (aminobenzenesulfonic acid) is diazotized and subjected to coupling reaction with o-aminobenzyl benzoate under acidic conditions. (b) The compound obtained in the above (a) is dissolved in (N-methyl) =嗣) and other non-f-substantial wealth, in the presence of carbon _ nitro abbreviated methyl chloride reaction, and obtain a guanamine compound. (b) above, the compound is obtained in water, ☆ compound '虱化纳进仃 (4), Obtained as the following pigment (2)) [Chem. 89] 312XP / invention specification (supplement) / 96-11/96119266 118 200815533 IS: The improvement of the polarizing performance, and the production of an anisotropic pigment film having various hue ^ ^ ^ The solvent used in the composition for the pigment film is preferably water, an organic solvent having water mixture 2, or a mixture thereof. The organic solvent may be exemplified by decyl alcohol, ethanol, or the like. Alcohols such as propanol, glycols such as ethylene glycol and diethyl-::: methicillin, ethyl sirosu, etc. A long-standing agent such as an aprotic solvent such as sulphur, t 疋阙 or N' N-dimethylformamide or a mixed solvent of two or more kinds. The concentration at the time of dissolving in these solvents is also dependent on the pigment. The concentration of the solution or the "large state" is preferably 0.001% by weight or more, more preferably 0.001% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1%. Below weight%. In order to increase the solubility of the pigment in the composition for the purpose of the pigmented film, it is necessary to add an additive such as a surfactant. The surfactant, I also uses any-interface activity in the anionic, cationic or nonionic system. 01% by weight or more, i. Below weight%. Material 2 = a composition for an anisotropic pigment film, and an additive may be used as needed in order to improve the naturalness of the substrate. Specific = editing; new dye processing lectures η volume • color Π 共 共 出版 出版 出版 、 、 、 、 6 6 6 6 6 6 6 6 6 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 251 "The interface chemistry of the agent" 312XP / invention manual (supplement) / 96-11 used in dyeing of fibers described in Chengwentang Shin Kong Co., Ltd., issued on September 5, 1963, pages 94 to 173, etc. /96119266 m 200815533 = coloring agent, and its method or the aforementioned surfactant, alcohol, glycol urea 'inorganic salt of sodium chloride, sodium sulfate and the like. The concentration thereof is preferably 0.01% by weight or more and 1% by weight or less. [6] Anisotropic pigment film An azo pigment dye film for anisotropic pigment film of the present invention can be used. The anisotropic dye film may contain other dyes, such as a known blue dichroic dye, iodine or the like, or a surfactant as described above, in addition to the azo dye for the anisotropic dye film of the present invention. additive. Of course, the pigments represented by the azo dyes of the anisotropic dye film of the present invention may be combined and contained. Examples of the method for producing the anisotropic dye film include the following methods (&amp;). (a) a method of dyeing a polymer substrate such as a polyvinyl alcohol or the like by a solution containing a dye (a composition for an anisotropic dye film), or a solution containing a dye (a composition for an anisotropic dye film) After the polymer base material such as polyvinyl alcohol is dyed, the method of stretching (C) dissolves a polymer substrate such as polyvinyl alcohol in a solution containing a dye (an anisotropic dye film component) #solution towel, When the filament is formed into a film and then stretched, when an anisotropic dye film is formed using the azo dye of the anisotropic dye film of the present invention, for example, in any of the methods (a) to (c) above, The azo pigment is dissolved in a suitable solvent for use. The solvent may, for example, be a solvent contained in the composition for an anisotropic dye film. 312XP/Invention Manual (Supplement)/96-11/96119266 124 200815533 Further, in the uranium method (a), (b), the substrate dyed with the dye solution, f is simultaneously treated with the pigment in the method (c) above. The substrate to be stretched may be a polyvinyl alcohol resin, a polyvinyl acetate resin 'ethylene/vinyl acetate WA resin, a nylon resin, a polyester resin or the like. Among them, a polymer material having a high affinity with a pigment such as polyvinyl alcohol is preferred. The type of polyvinyl alcohol is generally high in molecular weight and high degree of deuteration from the viewpoint of optical characteristics such as polarization degree and dichroism. However, in order to suppress shrinkage due to temperature and humidity, or A polyvinyl alcohol derivative which can appropriately adjust the type of the dichroic substance and the degree of deuteration or modification of the polyvinyl alcohol (hydrophobic copolymerization ratio) can be selected depending on the optical properties and the environmental resistance. The specific method for controlling the interaction between the polymer material and the pigment will accept the proton in the proton-proton--, -2, -R, -NHC0-, -NHC0NH-, etc. in the respective polymer materials and pigments. An aromatic Ru ring such as N=zN, —〇H, —Li 2, —NRR′, —〇R, —CN, —CsC—and a phenyl or naphthyl group is used as a functional group. It is made effective (R and R are arbitrary substituents). Further, by adjusting the density of the functional group, the effect of improving dichroism or dyeability is obtained. In the above methods (a) to (c), dyeing, film formation and stretching can be carried out by the usual methods described below. In the dye bath in which the above-mentioned composition for an anisotropic pigment film and an inorganic salt such as sodium chloride or sodium sulfate or a dyeing assistant such as a surfactant are added as needed, the temperature is usually 35 ° C or higher, usually 80 ° C. Hereinafter, the polymer film is usually immersed in 10 minutes or less to be dyed, and then, if necessary, 3 UXP/invention specification (supplement)/96-11/96119266 125 200815533 / or Erli into the cognac. Alternatively, the high molecular polymer is dissolved in water and a hydrophilic organic solvent such as glycerin or dimethyl propylamine, and the composition for anisotropic sinusoidin film of the present invention is added for dyeing the stock solution, , machine extension method, solution coating method, extrusion product house] ^ also pulled out the sheep to form the film to form a film. Dissolved in the solvent, the concentration of the sub-polymer is the same as the type of the knife-container, which is usually 5 to 10% by weight or more, usually 3 ί) # θ„/ν early and 1 terracotta Μ 30 weight (four) or less, preferably 20 weight: two / Λ 'concentration of the pigment dissolved in the solvent, usually relative to the two ... ', above, preferably U weight % difilament 'usually 5% by weight or less, preferably 25 5% by weight or less to 0. The film is formed into an unstretched film, which is extended in an axial direction by an appropriate method. The treatment is carried out to match the pigment molecules and the second method: the method of extending the color of the color c 4 in the axial direction, the method of stretching by the wet method: stretching, and the method of stretching by the dry method,

The method of performing compression between rolls and the like can be carried out by any method. The elongation rate is f times or more and 9 times or less 'But when polyglycolol and its derivatives are used as the high molecular polymer, the range is 3 ^ □ M d 仏 or more and 6 times or less. After the extension alignment treatment, boric acid treatment is carried out in order to improve the durability of the stretched film and improve the degree of polarization. By the treatment, the light transmittance and the degree of polarization of the pigment film of the f are improved. The conditions for the boric acid treatment vary depending on the type of the hydrophilic polymer and the coloring matter, but the boric acid wave is usually 1% by weight or more, preferably 5% by weight or more, and 9^ 1/ 96119266 126 200815533 The degree of privacy is usually 15% by weight or less, preferably 10% by weight or less. The temperature 'is usually 3 (rc or more, preferably 5 (rc or more, L is 80 c or less, preferably when the boric acid concentration is not full) or the weight is less than 30 C. The effect is poor, and when the shed acid concentration exceeds 15% by weight or the treatment temperature exceeds 8 Å or more, the anisotropic pigment film becomes brittle and thus is not preferable. The anisotropy obtained by the methods (a) to (4) The film thickness of the pigment film is usually 乂50 /zm or more, especially 8 〇&quot; m or more is preferably less than melon, especially 100 // m or less. + Containing the anisotropic pigment film azo pigment in this month The anisotropic pigment film is used as a function of obtaining a polarizing film such as linearly polarized or round elliptically polarized light by utilizing the anisotropy of light absorption, and can be utilized by the treatment of a substrate or a composition containing a pigment. As a function of various anisotropic films such as refractive index anisotropy 2 or conduction anisotropy, it can be made into a polarizing element suitable for various kinds of applications. When the anisotropic dye film is used as a polarizing element, it can be used. Anisotropic pigment prepared by the method represented by the above (4) to (C) Further, it is also possible to form a laminated layer having various layers such as a two-adhesive layer, a reflection preventing layer, a phase difference layer, and the like, and use the laminated body to form the anisotropic pigment film of the present invention. As a polarizing element, it is used to directly form the (four) element film, and

In addition to the above-mentioned protective layer, the function as an adhesion layer, an antireflection layer, an alignment film, and a phase difference film can be used as a function of a brightness increasing film by a wet film formation method or the like. The function of the reflective film, as a semi-transmissive reflective film machine: 312XP/#_g Mingshu (supplement)/96·ΐ 1/96Π9266 127 200815533 Yes, as a function of the diffusion film, the energy layer can be accumulated. The layer of the *manufacturer has a variety of mechanisms for use as a laminate. Eight have the formation of such optical functions. For example, the straw is made by various methods such as the following: #号差::机日^ ^ # This patent brother 3094113, such as the extension of the process, or the temple τ, the 卞 卞 夕 只 轭 Japanese patent It is formed by the processing of τ圮, such as the 3168850. Having a function as a function of a brightness-increasing film, for example, a micropore can be formed by a method as described in Japanese Patent Laid-Open Publication No. Hei No. 003:29030, or It is formed by superimposing two or more layers of cholesteric liquid crystal layers having different wavelengths of the center wave different from the π π ^ 曰 ... which are selectively reflected. "A layer having a function as a reflective film or a semi-transmissive film can be formed by using a metal film obtained by a method such as ruthenium plating or sputtering. Lu has a function as a function of a diffusion film, and can be contained by The resin solution of the microparticles is formed by being applied to the protective layer. Further, it has a function as a phase difference film or an optical compensation film, and liquid crystallinity such as a discotic liquid crystalline compound or a nematic liquid crystal compound can be used. The compound is coated and aligned to form a compound. The anisotropic dye film using the azo dye of the anisotropic dye film of the present invention can exhibit a wide range of colors, and a polarizing element having high heat resistance can be obtained. It can be applied not only to liquid crystal displays or organic EL displays, but also to liquid crystal projectors or display panels for vehicles, etc., which are required to have high resistance to 312XP/invention manual (supplement)/96-11/96119266 128 200815533. EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as it does not exceed the gist thereof. Wind again, in the following examples The transmittance of the anisotropic pigment film is measured by a spectrophotometer in which the prism polarizer is disposed in the incident light system, and then the dichroic ratio is calculated according to the following formula: One color ratio (D) = Az/Ay ® Az = - L〇g(Tz)

Ay= - log(Ty)

Tz: transmittance of polarizing film in the absorption axis direction of the dye film Ty: transmittance of the pigment film in the direction of polarization axis [Example 1] 1200 parts by weight of N-methylpyrrolidone was dissolved in 198 parts by weight in the following formula To the compound represented by (ia), 67 parts by weight of sodium carbonate and 117 parts by weight of p-nitrophenylhydrazine chloride were added, and the mixture was reacted at 201: for 1 hour. [Chem. 96] Produce qgm3 and then 'add 800 parts by weight of water, heat to 5 5~6 0 C ' Add 7 9 parts by weight of sodium hydrosulfide (purity 70%), keep the temperature at 55~60 °C The reaction was carried out for 1 hour, and 312XP/invention specification (supplement)/96_11/96119266 129 200815533, which is represented by the following formula (Bu), was obtained as the sodium salt. In the aqueous solution of the pigment, the maximum absorption wavelength (Amax) at i 〇 ppm was 368 nm. [化97]

• [Example 2] Under acidic conditions of hydrochloric acid, 12 parts by weight of sodium nitrite obtained by the method of the above Example 1 was added to 12 parts by weight of sodium nitrite to carry out diazotization on alkaline Under the conditions, a coupling reaction with 16 parts by weight of m-cresol was carried out, whereby the intended coloring matter No (i-2) represented by the following formula (i_2) was obtained as a sodium salt. In the aqueous solution of the pigment, the maximum absorption wavelength (Amax) at 1 〇 ppm was 384 nm. • [Zero 98] Heart. H &quot; OCH3 [Example 3] Under acidic conditions of hydrochloric acid, in 67 parts by weight of the sodium salt of the above-mentioned Example = pigments, 12 parts by weight of hydrazine was added, and under alkaline conditions and 21 parts by weight were cut. The acid was subjected to the reaction of the product of the formula (i-3) represented by the following formula (Η) in the form of a sodium salt by the reaction of the oxime = 312XP / invention specification (supplement) / 96-11/96119266 13 〇 200815533. In the aqueous solution of the pigment, the maximum absorption wavelength (λ max) of * ι〇qing is 375 nm.

[化99J

JCOQH

^nhQ^dh &lt; I -3) [Example 4] Under the acidic condition of hydrochloric acid, 52 parts by weight of amino acid di-nano(6-amino 1'3 mono-acid monosodium) was added The sodium nitrite was subjected to diazotization in a weight ratio, and a coupling reaction was carried out under acidic conditions with 36 parts by weight of sodium cerium-(2-methoxyphenyl)aminomethylrhodium. Nitrogen oxide was added to the system, and under the conditions of the test, the reaction was carried out for 5 hours at 7 (TC), whereby a compound represented by the following formula 0 (i-b) was obtained.

Na03:

(I

N3O3S The compound (i-b) was dissolved in 200 parts by weight of N-decylpyrrolidone, and 12 parts by weight of sodium carbonate and 20 parts by weight of p-nitrobenzoguanidine chloride were added, and the reaction was carried out at 2 ° C for 1 hour. Then, add 8 parts by weight of water, raise the temperature to 55~6 (rC, add 21 parts by weight of sodium hydrosulfide (purity 70%), the temperature will be 312XP / invention manual (supplement) / 96]! Ship Hall 6 131 200815533 The reaction was carried out at 55 to 6 ° C for 1 hour, and the intended pigment No. (i-4) represented by the following formula (i-4) was obtained as a sodium salt. The aqueous solution of the pigment was at 10 ppm. The maximum absorption wavelength (Amax) is 379 nm.

[Example 5] Under acidic conditions of hydrochloric acid, 117 parts by weight of the sodium salt of the pigment No. (i-4) obtained by the method of the above Example 4 was added with 15 parts by weight of sodium nitrite for diazotization, and alkalized. The coupling reaction with 21 parts by weight of indole phenol was carried out under the neutral conditions. The target pigment No. (i -5 ) represented by the following formula (i-5) was obtained in the form of a sodium salt. In the aqueous solution of the pigment, the maximum absorption wavelength (max) at 1 〇 ppm is 391 nm. [化102]

[Example 6] 312XP / invention manual (supplement) / 96-11/96119266 132 200815533 Under the acidic condition of hydrochloric acid, the weight of the 丨丨 7 weight is grasped by the main body. : The sodium salt of the pigment Ν〇.(1-4) is added with 15 parts by weight of sodium nitrite, and the coupling reaction with 27 parts by weight of salicylic acid is carried out under the test conditions, and the following is obtained as the sodium salt. The coloring matter No. (i-6) represented by the above formula (i 6). The aqueous solution + of the dye has an absorption wavelength (Amax) of 375 nm.

C i -β) [Example 7] 179 parts by weight of sodium 4-amino-1,1'-azobenzene-3,4,disulfonate was dissolved in 1000 parts by weight of fluorene-decylpyrrolidone Adding 58 parts by weight of sodium sulphate and 102 parts by weight of p-nitrobenzoguanidine chloride, and reacting at 2 (rc for 1 hour). Then, adding 4000 parts by weight of water, heating to 55 to 6 Torr. 〇, adding 165 parts by weight Sodium thiosulfate (purity: 70%) was reacted for 1 hour while maintaining the temperature at 55 to 60 ° C, and the intended coloring matter No. (b 7) represented by the following formula (i-7) was obtained as a sodium salt. In the aqueous solution of the pigment, the maximum absorption wavelength (Amax) at 1 〇 ppm is 355 nm. 312XP/Invention Manual (supplement)/96-11/96119266 133 73 200815533 [Chem. 104] hg3s~0k

So$h [Example 8] Under acidic conditions of hydrochloric acid, 87 parts by weight of the sodium salt of the pigment No. (i-7) obtained by the method of the above Example 7 was added with 13 parts by weight of sodium nitrite for diazotization. The coupling reaction with 18 parts by weight of decylphenol was carried out under basic conditions to obtain the intended coloring matter No. (i-8) represented by the following formula (i-8) in the form of a sodium salt. In the aqueous solution of the dye, the maximum absorption wavelength (λ max) at 1 〇 ρρηη was 373 nm. [化105]

&lt;i-8&gt; [Example 9] Under acidic conditions of hydrochloric acid, 15 parts by weight of sodium nitrite was added to 87 parts by weight of the sodium salt of the pigment No. (i-7) obtained by the method of the above Example 7 Diazotization, coupling reaction with 23 parts by weight of salicylic acid under basic conditions, thereby obtaining a target σ 312 ΧΡ / invention specification (supplement) / 96-11 in the form of a sodium salt represented by the following formula (i-9) /96119266 134 200815533 The maximum pigment No. (i-9) at ppm. The absorption wavelength (also max) in the aqueous solution of the pigment is 3 6 8 ηιη. [化106]

[Example 10] Under acidic conditions of hydrochloric acid, a denier was added to 67 parts by weight of the sodium salt of the dye No. (i-1) obtained by the method of the above Example 1 in the manner of Bu, +, Fen &gt; Under the conditions of the test, the coupling reaction with 17 parts by weight of isophthalic acid is carried out, whereby the intended coloring matter M〇. (i-10) represented by the following formula (丨-1〇) is obtained in the form of a sodium salt. . The maximum absorption wavelength (Umax) of the aqueous solution of the pigment was 420 nm. [化107]

〇CH3

HO ί -10) [Example 11], under the acidic conditions of f acid, added 12 parts by weight to 67 parts by weight of the sodium salt of the pigment No. (i-1) of the above-mentioned Example 1. Nitrous acid 312XP / invention manual (supplement) / 96-11/96119266 135 200815533 Sodium is diazotized, under the conditions of the test, the sputum is used to carry out the S reaction. The form of the sodium salt is obtained by the following formula (i-I), and the pigment No. (i-ll). The maximum absorption wavelength (Amax) of the aqueous solution of the pigment was 1 387 nm. [化108]

OCHz (i to 11) [Example 12] 12 parts by weight of sodium nitrite was added to 67 parts by weight of the sodium salt of the pigment No. (i-Ι) obtained by the method of the above Example 于 under acidic conditions of hydrochloric acid. Diazotization is carried out, and a coupling reaction with 22 parts by weight of guaiac (o-decyloxyphenol) is carried out under the conditions of the test, whereby the purpose of the following formula (i-12) is obtained in the form of a sodium salt. Pigment No. (i-12). In the aqueous solution of the pigment, the maximum absorption wavelength Umax at 10 ppm was 39 brilliant. [109]

(I 13⁄4 312XP/Invention Manual (Supplement)/96-11/96119266 136 200815533 [Example 13] Under acidic conditions of hydrochloric acid, in 35 parts by weight of p-aminobenzenesulfonic acid (4-aminobenzenesulfonic acid) Adding 15 parts by weight of sodium nitrite for diazotization, and coupling with 48 parts by weight of sodium N-(2-decyloxyphenyl)aminosulfonate under acidic conditions. Adding sodium hydroxide to the system The reaction was carried out under an experimental condition at 85 ° C for 1 hour, whereby a compound represented by the following formula (i - c) was obtained.

The compound (i-c) is dissolved in 400 parts by weight of N-mercaptopurine|same, and 23 parts by weight of sodium carbonate and 20 parts by weight of p-octylbenzoquinone chloride are added, and the mixture is carried out at 2 ° C. 1 hour reaction. Then, adding 100 parts by weight of water and then raising the temperature to 55 to 60 ° C, adding 15 parts by weight of sodium thiosulfate (purity 70%), maintaining the temperature at 55 to 60 ° C for 1 hour, and using sodium salt The form of the pigment No. (i-13) which is represented by the following formula (i-13) is obtained. In the aqueous solution of the pigment, the maximum absorption wavelength (λ max) at 1 〇 ppm was 367. [111]

312XP/Invention Manual (Supplement V96·*11/96119266 137 200815533 [Example 14] Under the acidic condition of hydrochloric acid, the pigment obtained by 90 parts by weight of the method...the sodium sulphate is subjected to diazotization under the test conditions. 22 parts by weight of the inter-molecular coupling reaction, thereby obtaining the desired coloring matter N〇. (i-(4) in the form of a sodium salt. The maximum absorption wavelength (max) of the aqueous solution of the pigment is 1 383 nm. [化112] H〇3S-^^

Och3 [Example 15] Under acidic conditions of hydrochloric acid, 15 parts by weight of sodium nitrite was added to 35 parts by weight of p-aminobenzenesulfonic acid (4-amino ruthenium acid) for diazotization under acidic conditions. 45 parts by weight of sodium N-(3-methylphenyl)aminomethanesulfonate was subjected to a coupling reaction. Sodium hydroxide was added to the system at 85 under test conditions. The reaction was carried out for 10 hours, whereby a compound represented by the following formula (i-d) was obtained. [化113]

(fd) 3 UXP/Invention Manual (Supplement)/96-11/96119266 138 200815533 The compound (id) is dissolved in 300 parts by weight of N-methylpyrrolidone, and 15 parts by weight of sodium carbonate and 27 parts by weight are added. Nitrobenzoquinone chloride was reacted at 2 ° C for 1 hour. Then, adding 1 000 parts by weight of water, heating to 55 ~ 60C 'adding is part by weight of sodium thiosulfate (purity 70%), maintaining the temperature at 55~6 〇t: reaction for 1 hour, and obtaining as sodium salt The intended coloring matter No. (i-15) represented by the following formula (l-15). The maximum absorption wavelength (max) of the aqueous solution of the pigment at 1 〇 ppm is 360 nm. [Example 114] Under acidic conditions of hydrochloric acid, 13 parts by weight of sodium salt of nitrous acid was added to 79 parts by weight of the sodium salt of the pigment No. (i-13) obtained by the method of the above Example 13 By nitriding, a coupling reaction with 19 parts by weight of resorcin is carried out under alkaline conditions, whereby the intended coloring matter No. (i-16) represented by the following formula (i-16) is obtained as a sodium salt. In the aqueous solution of the pigment, the maximum absorption wavelength (Amax) at 1 〇 ppm was 425 nm. [化115]

312XP/Invention Manual (Supplement)/9641/96119266 139 200815533 [Example 17] The dye N was obtained in 79 parts by weight of the method of the above Example 13 under acidic conditions of hydrochloric acid. - 13 parts by weight of nitrous acid is added to the sodium salt of (1-13), and sodium diazotization is carried out to carry out a coupling reaction with 19 parts by weight of o-cresol under basic conditions, thereby obtaining the following in the form of a sodium salt The formula (heart rate... The maximum absorption wavelength (Amax) in the aqueous solution of the pigment is 382 nm. [Chem. 116] ho3s

c 1-17) [Example 18] Under acidic conditions of hydrochloric acid, 13 parts by weight of sodium nitrite was added to 79 parts by weight of the sodium salt of the dye No. (I-13) obtained by the method of the above-mentioned Example 13 Diazotization, coupling reaction with 22 parts by weight of guaiacol (o-nonyloxyphenol) under alkaline conditions, thereby obtaining a pigment ν 以 represented by the following formula (i-18) in the form of a sodium salt · (i-18). In the aqueous solution of the pigment, the maximum absorption wavelength (Amax) at 10 ppm was 39 〇 nm. [化117] ho3s

Och3

C 1-18) 312XP/Invention Manual (Supplement)/96-11/96119266 140 200815533 [Example 19] Under the acidic condition of hydrochloric acid, the pigment No. (i) obtained by the method of the above Example 7 was obtained in 89 parts by weight. -7) the sodium salt is added to 13 parts by weight of nitrous acid steel for diazotization, and is subjected to coupling reaction with 21 parts by weight of guaiacol (o-methoxyphenol) under basic conditions, thereby taking the form of sodium salt. The intended coloring matter No. (i-19) represented by the following formula (1-19) was obtained. In the aqueous solution of the pigment, the maximum absorption wavelength (max) at 10 ppm was 374 nm. [化118]

H〇aS

CI-19&gt; [Example 20] 16 parts by weight of sodium 4-aminoazobenzene-4,-sulfonate was dissolved in 1 part by weight of N-decylpyrrolidone, and 5 parts by weight was added. Sodium carbonate, 12·8 heavy wounds were reacted with nitrobenzionic acid gas at 50 ° C for 1 hour. Then, 500 parts by weight of water was added, and the temperature was raised to 55 to 6 (rc, 8 wt. parts by weight of sodium hydrogen sulfide (purity: 70%) was added, and the temperature was maintained at 55 to 60 ° C for 1 hour, and after cooling, filtration was carried out. The compound was washed with 2% by weight of saline to obtain a compound represented by the following formula (i_e).

312XP/Invention Manual (Supplement)/96-11/96119266 141 200815533 8.4 parts by weight of the above compound (Bu e) is dissolved in 13 parts by weight of N-methylpyrrolidone, 20 parts by weight of water under acidic conditions of hydrochloric acid Addition of i 5 parts by weight of sodium nitrite for diazotization, coupling reaction with 5 parts by weight of N-(4-carboxybenzyl)aniline under acidic conditions, thereby obtaining the following formula (i-20) in the form of a sodium salt ) The intended color No. (i-20). The maximum absorption wavelength (max) at 10 ppm in the aqueous solution of the pigment was 354 nm. [化120]

[Example 21] Under acidic conditions of hydrochloric acid, 8.7 parts by weight of p-aminobenzenesulfonic acid (4-aminobenzenesulfonic acid) was added with 3.6 parts by weight of sodium nitrite for diazotization, in acidity conditions. The coupling reaction was carried out with 11.2 parts by weight of 1,7-climate acid ((:16乂6,3&amp;(1)(8-aminonaphthalene-2-sulfonic acid). Sodium argon oxide was added to the system, Under the conditions of the test, 16.6 parts by weight of p-nitrophenylhydrazine chloride was added, and the reaction was carried out for 5 hours at 6 ° C and pH 8. After the reaction, η. 7 parts by weight of sodium hydrogen sulfide (purity 70%) was added. The reaction was carried out at 60 ° C for 1 hour to obtain a compound represented by the following formula (b): 312XP / invention specification (supplement) / 96-11/96119266 142 200815533 [Chemistry 121]

(i-f) SO is run under acidic conditions of hydrochloric acid, and is added to 7.5 parts by weight of the above compound (i-〇, 73 parts by weight of sodium nitrite for diazotization, under test conditions and 1.08 weight The indole phenol is subjected to a coupling reaction, whereby the objective dye N〇. (i-21) represented by the following formula (i-21) is known as a sodium salt. The aqueous solution of the pigment is the largest at 1 〇 PPm. The absorption wavelength (Amax) is 379 nm.

[Example 22] Under acidic conditions of hydrochloric acid, 5.7 parts by weight of the above compound (if) was added with 0.3 parts by weight of sodium nitrite to carry out diazotization under alkaline conditions with 〇·98 parts by weight 3- Methyl-3-hydrazine is subjected to a coupling reaction, whereby a coloring matter No. (1 22) represented by the following formula (i-22) is obtained as a sodium salt. In the aqueous solution of the pigment, the maximum absorption wavelength (λ max) at 1 为 is 407 ηπι 〇 312XP / invention specification (supplement) /9641/96119266 143 200815533 [Chemistry 123]

(ί 2 2 [Example 2 3 ] Adding 0.05 parts by weight of the sodium salt of the pigment of the pigment No. (il) and 〇. 〇 2 parts by weight of anhydrous sodium sulfate in 1 〇〇 heavy wound water, mixing and dissolving ^Staining solution. A polyvinyl alcohol film (porous film) made by Nippon Synthetic Chemical Industry Co., Ltd. was immersed in 5 (TC staining solution) for staining for the time indicated in Table 1, and the remaining dye was washed in 50 = water bath. In the 4% by weight rotten acid water solution, it is extended to 6 times. After stretching, the remaining boric acid is washed in a water bath at room temperature, and air-dried to obtain an anisotropic pigment film. The absorption wavelength of the anisotropic pigment film and the monomer ♦ transmittance at the wavelength thereof and the dichroic ratio are described as having a high color: [Example 24] 0.05 weight is added to 1 〇 0 liters of distilled water. Part of the pigment N〇 (i-2) = the pigment of the nano and U2 parts by weight of anhydrous sodium sulfate, _ dissolved, made into a dyeing solution. The polyester film (sail film) made by Sakamoto Synthetic Chemical Industry Co., Ltd. The recorded time was soaked in 5 (r staining solution for dyeing, and the remaining dye was removed in a separate C water bath. After that, the 95 wt% of the 4 wt% rotten saponin solution was extended to 6 times. After the extension, the remaining boric acid was washed in a water bath at room temperature, and air-dried to obtain an anisotropic pigment film. 312XP / stomach description (supplement) / 96-11/96119266 144 200815533 The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the two-color ratio at the wavelength are shown in Table 1, and it is known that the color has a high color [Example 25] 90.05 parts by weight of a sodium salt of a pigment of pigment N〇(i_3) and 10 parts by weight of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.: GL-05) were added to 90 parts by weight of water. After stirring and dissolving in a water bath, the film was expanded to a thickness of about 1 to dry, thereby obtaining a film of a polyvinyl alcohol (pm) containing a pigment. The PVA film was immersed in a 5 wt% aqueous solution of boric acid, and then stretched to Lu. 3 times, an anisotropic pigment film is obtained. The maximum absorption wavelength (max) of the anisotropic pigment film is 405 nm, which is known to have a high dichroic ratio. [Example 26] In Example 25, except for the pigment Pigment N〇. The pigment of (i_3) is changed to the sodium salt of the pigment of pigment No. (i-4) Further, a polyvinyl alcohol (pvA) film containing a pigment was obtained in the same manner as in the method described in the Examples. The PVA film was immersed in a 5 wt% aqueous solution of boric acid, and then stretched to 3 times to obtain It is understood that the anisotropic dye film has a maximum absorption wavelength (Amax) of 411 nm and a high dichroic ratio. [Example 27] A sodium salt of a pigment other than the pigment No. (i-5) was used. In the same manner as in Example 24 except that the dyeing time was set to the dyeing time described in Table 1, an anisotropic dye film was obtained in the same manner as in Example 24. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are described in the Table, and it is known that the color ratio is south. 312XP/Invention Manual (Supplement)/96-11/96119266 145 200815533 [Example 28] The use of the sodium salt of the dye of the dye No. (i_6) and the dyeing time are set to the dyeing time described in Table 1, An anisotropic dye film was obtained in the same manner as in Example 24. The maximum absorption wavelength of the anisotropic dye film and the early body transmittance at a wavelength of 5 Hz and the dichroic ratio are shown in Table 1, and it is known that the color ratio is high. [Example 29] Except that in Example 25, the dye was changed from the dye of the dye No. (i-3) to the sodium salt of the dye of the dye No. (i-7), and the rest was the same as in Example 25. In the same manner as the method described, a polyvinyl alcohol (pVA) film containing a pigment was obtained. The PVA film was immersed in a 5 wt% aqueous solution of boric acid, and then stretched to 3 times to obtain an anisotropic dye film. The maximum absorption wavelength (λ max) of the anisotropic dye film was 384 nm, and it was found to have a high dichroic ratio. [Example 30] Anisotropy was obtained by the same method as in Example 24 except that the sodium salt of the dye of the dye No. (i-8) was used and the dyeing time was set to the dyeing time of Table 1 Pigment film. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are described in the Table, and it is known that the color ratio is high. [Example 31] An anisotropic dye film was obtained by the same method as in Example 24, except that the sodium salt of the dye of the pigment N0. (i-9) was used, and the dyeing time was set to the dyeing time described in Table 1. The maximum absorption wave 312XP of the anisotropic pigment film/invention specification (supplement)/9641/96119266 146 200815533 and the monomer transmittance and the dichroic ratio at the wavelength are described in the table, and it is known that the color ratio is high. . [Example 32] An anisotropic dye film was obtained in the same manner as in Example 24 except that the sodium salt of the dye of the pigment No. (i-l) was used, and the dyeing time was set to the dyeing time described in Table 1. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are described in the Table, and it is known that the color ratio is south. [Example 33] An anisotropic dye film was obtained by the same method as in Example 24, except that the sodium salt of the dye of the pigment No. (i-ΙΙ) was used, and the dyeing time was set to the dyeing time described in Table 1. . The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are shown in Table}, and it is known that the color ratio is south. [Example 34] # An anisotropic dye film was obtained by the same method as in Example 24 except that the sodium salt of the dye of the dye No. (丨-12) was used, and the dyeing time was set to the dyeing time described in Table 1. . The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are shown in Table i, and it is known that the color ratio is high. [Example 35] An anisotropic pigment film was obtained in the same manner as in Example 24, except that the sodium salt of the dye of the pigment No. (i-13) was used, and the dyeing time was set to the dyeing time of Table 1 . The maximum absorption wave 312XP of the anisotropic pigment film/invention specification (supplement)/96-11/96119266 147 200815533 and the monomer transmittance and the dichroic ratio at the wavelength are described in the table, and it is known that焉 two color ratio. [Example 36] An anisotropic dye film was obtained by the same method as in Example 24 except that the sodium salt of the dye of the pigment No. (i-14) was used, and the dyeing time was set to the dyeing time described in Table 1. . The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are described in the Table, and it is known that the color ratio is high. Lu [Example 3 7] Anisotropy was obtained by the same method as in Example 24, except that the sodium salt of the dye of the pigment No. (i -15) was used, and the dyeing time was set to the dyeing time shown in Table 1 Pigment film. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are shown in Table 1, and it is known that the color ratio is high. [Example 38] φ An anisotropic dye was obtained by the same method as in Example 24 except that the sodium salt of the dye of the dye No. (i-16) was used, and the dyeing time was set to the dyeing time of the redundant loading of Table 1. membrane. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are shown in Table 1, and it is known that the color ratio is high. [Example 3 9] An anisotropic dye was obtained in the same manner as in Example 24 except that the sodium salt of the dye of the pigment No. (i-π) was used, and the dyeing time was set to the dyeing time described in Table 1. membrane. The maximum absorption wave of the anisotropic pigment film 312XP/F Monthly Specification (Supplement) m96i 148 200815533 The monomer transmittance at the wavelength is known to have a high dichroic ratio. [Example 4 0 ] and the two color ratios are shown in Table 1, except that the sodium salt of the dye of the dye No. (Bu 18) was used, and the dyeing time was set to the wood color time of Table 1 and 24 The same method was used to obtain an anisotropic f-growth pigment film. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are shown in Table i, and it is known that the color ratio is high. 10 [Example 41] The sodium salt of the dye of the dye No. (Bu 19) was used, and the dyeing time was set to the dyeing time described in Table 1, and the anisotropy was obtained by the same method as in Example 24 Pigment film. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are shown in Table i, and it is known that the color ratio is high. [Example 42] A dye N was used. The sodium salt of the pigment of (Bu 2) was used, and the dyeing time was set to be the same as the dyeing time described in Table 1, and the soybean meal was the same as that of Example 24. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at a wavelength of 3 Hz are described in the Table, and it is known that the color ratio is high. [Example 43] =,. (Sa 21) the sodium salt of the dye, and the dyeing time was set to be the same as the other method. The same method as in Example 24 was used to give an anisotropic pigment film. The maximum absorption wave of the anisotropic pigment film 312 ΧΡ / _ _ (supplement) / 96-11 / 96219266 149 200815533 at the X-wavelength of the monomer transmittance and the two-color ratio are shown in Table 1, it is known that the high dichroic ratio . [Example 44] #1, the nano-salt of the dye of the pigment NQ·(Bu 22) was used, and the dyeing time was set to be the same as the second-color time, and the same or the same objective film was used as in Example 24. The maximum absorption wavelength of the anisotropic dye film, the monomer transmittance at the wavelength, and the dichroic ratio are described in the table, and it is known that the color ratio is south. •[Table 1]

[Examples] In 100 parts by weight of distilled water, the sodium salt of the pigment Νο·(ιι-1) represented by 0.02 parts by weight or less and the 〇 tongue type (u D • 无水 anhydrous 312 ΧΡ/invention specification (supplement) were added. ) /96-11/96119266 15〇200815533 Sodium sulphate was stirred and dissolved to prepare a dyeing solution. The polyethylation film (〇PL film) manufactured by Nippon Synthetic Chemical Co., Ltd. was immersed in the time indicated in Table 2 at _ dye = enter = Color, after washing the remaining dye in a (10) water bath, it is extended to 6 times in a 50C, 4% by weight aqueous solution of boric acid. After stretching, the boric acid is washed in (4), and dried to obtain an anisotropic Pigmented film =, the maximum absorption wavelength of the directional pigment film and the monomer transmittance and the dichroic ratio at (4) are shown in Table 2, which is known to have a high [Chemical 124]

pOOH J^OH &lt;a-i) [Example 46] The dyeing time is set to the dyeing shown in Table 2 except that the sodium salt 2 of the dye of the dye No. (ii-2) represented by the following formula (1) to 2) is used. Other than the time, the anisotropic pigment film was obtained by the same method as that of Bega 45. The maximum absorption wavelength of the anisotropic 1* green pigment film, the monomer transmittance at the wavelength, and the dichroic ratio are shown in Table 2, and it is understood that the dichroic ratio is high. [化 125]

312XP/Invention Manual (supplement)/96-11/96Π9266 151 200815533 [Embodiment 47]

In addition to the dyeing time of the following formula (ii-β + M, the pigment of the pigment No. (ii-3), and the dyeing time is set to 矣? The other method 3 [雈p wα + m ] was used to obtain an anisotropic pigment film in the same manner as in Example 45. The anisotropy and the dichroic ratio are shown in Table 2, and it was found that the ratio was high.

(a - 3) The maximum absorption wavelength of the pigment film and the monomer transmittance at the wavelength are [Chem. 126] [Example 48] except that the dye NQ (ii_4) represented by the following formula (ii-4) is used. The anisotropic dye film was obtained in the same manner as in Example 45 except that the dyeing time was set to the dyeing time described in Table 2. The maximum σ and the wavelength of the anisotropic dye film and the monomer transmittance at the wavelength are shown in Table 2 in terms of the two-color ratio, and it is understood that the color ratio is high. [化 127] ΗΟ

&lt;«—4] [Example 49] In addition to the use of the sodium salt of the dye of the dye No. (ii-5) represented by the following formula (Π-5), the non-sigma is set to the dyeing time described in Table 2 The rest of the use of the 312 job description (supplement) /% seven edit 2 leak 15533 Example 45 the same as the maximum absorption of the film to obtain anisotropic pigment film. The anisotropic color ratio is shown in Table 2, and the monomer transmittance at the wavelength and the chromaticity of the second color ratio are known to have a high dichroic ratio.

(I s&gt; [Example 50] Except that the following salt is used, the salt is shown: dye N〇. (ii, (4) is used in the same manner as in Example 45, and the rest is good. An anisotropic pigment film is obtained from the pigment film. The anisotropy and the two-color ratio are: the wavelength of the absorption and the monomer transmittance at the wavelength are [2] in Table 2 Color ratio.

CK-6&gt; 312ΧΡ/Invention Manual (Supplement)/96-11/96119266 200815533 [Table 2] Example 45 46 47 48 49 Pigment No. ii -1 ii - 2 ii - 3 ii - 4 ii-5 Dyeing time 1 ~~ Γ〇~^ 7 — 1 ~~ 1 Maximum absorption wavelength (nm) 400 475 410 385 Migration rate (%) 40 —^ 38 A __36 Two-color ratio 36 24 22 35 50 ii - 6 1 ft JU 420 —__44 43 21 25 [Example 51] 48 parts by weight of N-methylisonidine, 53 parts by weight of p-terpene bromide, 55 parts by weight of potassium carbonate, and 100 parts by weight of methylpyrrolidone were mixed' The reaction was carried out for 3 hours at 70 C. After the reaction was completed, water was added to the system, and the resulting crystals were collected by filtration. Under acidic conditions of hydrochloric acid, 29 parts by weight of sodium nitrite is added to 69 parts by weight of the aminobenzenesulfonic acid to be diazotized, and the crystal obtained in the above reaction is subjected to coupling reaction under acidic conditions, and the sodium salt is used. The objective dye No. (iii-Ι) represented by the following formula (iii-1) is obtained in the form. In the aqueous solution of the pigment, the maximum absorption wavelength (λ max) at 10 ppm was 443 nm. [Chem. 130]

Ciil -1 ) [Example 52] 35 parts by weight of N-methyl m-toluidine, 38 parts by weight of p-diphenylbenzene dibromide, 39 parts by weight of potassium carbonate, and 71 parts by weight of N-methylpyrrolidone were mixed. 312XP/Invention Manual (supplement)/96-11/96119266 154 200815533 The reaction was carried out at '70 C for 3 hours. After the reaction was completed, water was added to the system, and the resulting crystals were collected by filtration. Under acidic conditions of hydrochloric acid, 21 parts by weight of sub-phase was added to 64 parts by weight of 6-amino-2-naphthalenesulfonic acid; sodium disulfate was diazotized, and the coupling reaction was carried out under acidic conditions with the crystal obtained in the above reaction. In the form of a sodium salt, the intended coloring matter No. (iii-2) represented by the following formula (iii-2) is obtained. The maximum absorption wavelength (max) at 10 ppm in the aqueous solution of the pigment was 450 nm. [化131]

Cm-2) [Example 53] To 90 parts by weight of water, 5 parts by weight of a sodium salt of a pigment Ν〇·(ϋί-1), and 10 parts by weight of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd.) were added. : GL-05), dissolved in a water bath, and then spread to a thickness of about 1 mm, thereby obtaining a polyethylene glycol (PVA) film containing a pigment. The PVA film was immersed in a 5 wt% aqueous solution of boric acid, and then stretched to 3 times to obtain an anisotropic dye film. The maximum absorption wavelength (max) of the anisotropic pigment film is 454 nm, which is known to have a high dichroic ratio. [Example 54] To 90 parts by weight of water, 5 parts by weight of a pigment sodium salt of a pigment N〇 (iii-2), and 10 parts by weight of polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. 312XP/invention specification (supplement) ) / 96-11/96119266 155 200815533 Manufactured: GL-05), stirred and dissolved in a water bath, developed to a thickness of about _, dried, thereby obtaining a polyvinyl alcohol (pvA) film containing a pigment. The pvA film was immersed in a 5 wt% aqueous solution of boric acid, and then stretched to 3 times to obtain an anisotropic pigment film. The maximum absorption wavelength of the anisotropic dye film (again (4) is 459 nm, which is known to have a high dichroic ratio. [Example 55] 5 parts by weight of rhodium·quinone was added to 90 parts by weight of water to have a dye Νο· represented by the following formula (ίν_υ) (ίν-1) sodium salt, 1 part by weight of polyvinyl alcohol (manufactured by Sigma Chemical Industry Co., Ltd., GL-〇5), stirred and dissolved, and then spread to a thickness of about 1 mm 'dry' to obtain a pigment Polyvinyl alcohol (ρμ) film. The PVA film is immersed in a 5 wt% aqueous solution of boric acid and then stretched to 3 times to obtain an anisotropic pigment film. The maximum absorption wavelength of the anisotropic pigment film (λ max ) is 397 nm, which is known to have a high dichroic ratio.

Ψζ ch3 [Example 56] In addition to changing the sodium salt of the above dye No. (iv-Ι) to the sodium salt of the dye No. (i v-2 ) represented by the following formula (iv_2), the remaining use and implementation In the same manner as the method described in Example 5, a polyvinyl alcohol (pVA) film containing a pigment was obtained. 0 312 ΧΡ / invention specification (supplement) / 96-11/96119266 156 200815533 The PVA film was immersed in a 5 wt% aqueous solution of boric acid. And then stretched to 3 times to obtain an anisotropic pigment film. The maximum absorption wavelength (personal meaning) of the 5 angstrom anisotropic pigment film is 4 〇 5 nm, which is known to have a south dichroic ratio. [化133]

[Example 5 7] The use and the examples are the same except that the sodium salt of the above dye No. (iv-1) is changed to the sodium salt of the dye No. (iv-3) represented by the following formula (iv-3). 55 The same method was used to obtain a polyvinyl alcohol (pvA) film containing a pigment. φ The film was immersed in a 5 wt% aqueous acid solution, and then stretched to 3 times to obtain an anisotropic dye film. The maximum absorption wavelength of the anisotropic pigment film (also labeled as "423 nm, with a two-color ratio, is shown in the long-term durability of the temperature. South-wet state. [Chem.

312XP/Invention Manual (Supplement)/96-11/96119266 157 200815533 [Example 58] The sodium salt of the dye No.: The method described in Example 55 is the same as the 7 2 nano-salt and the other uses the solid alcohol (10) film. #_方法' Obtaining the pigment-containing polyethylene, soaking the PVA film in the tongue 3 times, and obtaining the difference (four) = then Stretching to the wavelength U position) is 417 ηιη, which is known to have a high and close [Chemical 135]

(铋―4) [Example 5 9 ]

To 90 parts by weight of distilled water, 1 part by weight of a polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) having a degree of polymerization of about 〇, (10) parts by weight of glycerol 'dissolved in a water bath (4) to obtain polyethylene _Aqueous solution. It was dried at room temperature for 6 hours to obtain a polyvinyl alcohol film (PVA film) having a film thickness of about 15 mil. Further, 5 parts by weight of a sodium salt of a pigment of the pigment (1-2) is added to the aqueous polyvinyl alcohol solution, and the mixture is stirred and dissolved at room temperature. The mixed solution of the pigment and polyvinyl alcohol is spread on a tray to a thickness of $100, and the color is added in /zm and then dried in a TC oven for 3 minutes. 312XP/Invention Manual (Repair) )/96-11/96119266 158 200815533 The 5 liter PVA film was immersed in a 4 wt 5% aqueous solution of lindic acid for 3 〇 minutes, and then stretched to 5 times at room temperature to obtain an anisotropic pigment film. The absorbance of the anisotropic dye film and the dichroic ratio at each wavelength are shown in Fig. 1. The maximum absorption wavelength (Amax) g of the anisotropic dye film is 4 〇 5 nm, which is known to have a high dichroic ratio. 0] Under acidic conditions of hydrochloric acid, 79 parts by weight of the sodium salt of the pigment (i-13) obtained by the method of the above Example 13 was added to 13 parts by weight of sodium nitrite for diazotization under alkaline conditions. 24 parts by weight of salicylic acid was subjected to a coupling reaction, whereby the target pigment N〇(i_23) was obtained in the form of a sodium salt. The maximum absorption wavelength (Amax) at 10 ppm in the aqueous solution of the pigment was 375 nm. ]

[Example 61] Under the acidic condition of hydrochloric acid, in the sodium bismuth of the pigment (i-1) obtained by the method of the above Example i in the tongue b7, the amount of the pigment (i -1) obtained in the above Example i was 12% by weight. Sodium diazotization was carried out under alkaline conditions, and 4 ^ t ^ ^ U was added to the summer phenol for coupling reaction. The pigment No. (i-24) was obtained in the form of sodium salt. In the aqueous solution of the pigment 312XP/invention specification (supplement)/96-11/96119266 159 200815533, the maximum absorption wavelength (human max) at 10 ppm is 367 nm ° [Chem. 137]

&lt; i - 24) • [Example 62] The same procedure as in Example 24 except that the sodium salt of the dye of the dye No. (i-23) was used, and the dyeing time was set to one or two. The method obtains an anisotropic pigment film. The maximum absorption wavelength of the anisotropic dye film and the monomer transmittance and the dichroic ratio at the wavelength are shown in Table 1, and it is known that the dichroic property is high. [Example 63]

The anisotropic dye film was obtained by the same method as in Example 24 except that the sodium salt of the dye of the pigment No. (i-24) was used, and the dyeing time was set to Table 1 and the dyeing time was carried out. It is known that the maximum absorption wavelength of the anisotropic dye film and the monomer transmittance at a far wavelength and the dichroic ratio have a dichroic property. [Comparative Example 1] In addition to using the pigment represented by the following formula (V-1), the sodium of the pigment of the main a, (v-1) of the inflammation is used as a coloring matter, and the dyeing time is set as Table 3 Except for the dyeing time of w war, the same method as in Example 24 was used to mast the anisotropic pigment film. 312XP / invention manual (supplement) / 96-11/96119266 160 200815533 - the maximum absorption wavelength of the anisotropic pigment film and the monomer transmittance at this wavelength and the two-color ratio table 3, we can see the two colors Sex is not sufficient. [化138]

[Comparative Example 2] (V -1) In addition to the use of a sodium salt of a dye of the pigment N〇 (v2) represented by the following formula (v-2) as a coloring matter, and the dyeing time as the color time of the fourth color (Table 4), the rest An anisotropic dye film was obtained in the same manner as in Example 24. The maximum absorption wavelength of the anisotropic dye film, the monomer transmittance at the wavelength, and the dichroic ratio are shown in Table 3'. The dichroism is not sufficient.

[化139]

(V — 2) 312XP/Invention Manual (Supplement y96-i 1/96119266 161 200815533 [Table 3] Comparative Example Pigment No. Dyeing Time (min) Maximum absorption wavelength (nm) Monomer transmittance (%) Two-color ratio 1 v-1 2 385 43 14 2 v-2 5 380 39 19 Furthermore, this application is based on the patent application filed on May 30, 2006 (Special Wishes 2006-1 50237), 2006 6 Japanese patent application (Japanese Patent Application No. 2006-182144), which was filed on the 30th of the month, Japanese patent application (Japanese Patent Application No. 2006-295340), which was filed on October 31, 2006, and Japanese patent application for delivery on May 30, 2006 Japanese Patent Application (Japanese Patent Application No. 2006-150272), which was filed on June 15, 2006, and Japanese Patent Application (Japanese Patent Application No. 2006-166284), which was filed on June 30, 2006 (Japanese Patent Application No. 2006-181) 060), all of which are referred to by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the absorbance of the anisotropic dye film obtained in Example 59 and the dichroic ratio at each wavelength.

312XP/Invention Manual (supplement)/96-11/96119266 162

Claims (1)

200815533 X. Patent application scope: i. An azo dye for an anisotropic pigment film, characterized in that the free acid form is represented by the following formula (1): (1) Formula (1), human and Α Each of which may independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a arylaromatic heterocyclic group which may have a pen/sheet substituent, or a group represented by the following formula (1-α) ; XI is shown in any one of the following formulas (1-a) to (1_c). [Chemical 141] Soil' (1 a) represents an oxygen atom or an NH group; an alkyl group which may have a substituent or may be bonded to form a ring; in the formula (l-α), 'Q11 and Q12, respectively, R91 and R92 independently represent a hydrogen atom, respectively. Amine group with substituents; 1^91 and R92 312XP/Invention Manual (supplement Μ6-〗 1/96119266 200815533 [Chemical 142] Ar1—Ν~χ2_Α|2_ I, “la) Food 3. -X3—Han, (I4&gt;) In the formula (l-a)~(1-C), χ2~γ4 -C〇-group; r~r are independently represented by the table - hydrogen:: independent -ch2-group or ~Ar6 respectively represent 丨, 4 - extension Benzoquinone di or ethyl; phenyl, 2,6-anthranyl or di-,-naphthyl, 1,5-extension, - a group represented by the following formula (1-al); The base 1,4 is not a base 1,5~, and the 2,6-extension-based group and the group represented by the following formula (Ι-al) may have a substituent; [Chem. 143] w.-l-ur % 1..I.MX tm) V jr In the formula (1-al), the ring α is a heterocyclic ring of 5 or 6 membered rings. 312 ΧΡ / invention manual (supplement) / 96-11/96119266 164 200815533 2. The azo dye for an anisotropic pigment film according to the first aspect of the invention, wherein the above formula (1-1) is represented by the following formula (1-1) 1) · · · [ 144] ίβ·* (1-1) Formula (i-υ, a21 represents i or two groups consisting of a sulfonic acid group, a carboxyl group, and a substituted alkoxy group a group selected from the group consisting of a phenyl or a naphthyl group; the earth is A22 a phenyl group which may have a substituent or a hetero group which may have a substituent; ",", χ2 and r are respectively the above formula (b) a) 曰美矢3.:: Please refer to the anisotropic pigment of the first item of the patent range: pigment, wherein the above formula (1) is represented by the following formula (1-2): opal color [化145] ? Ar'-N_G-Ar2 Η α-2) In the formula U-2), 'Ar1 and Ar2 respectively and the above formula (1 and independently represent the following formula (Bu(4)~(ι_2 is the same as K'^; 312XP/invention specification (complement) Piece)/96-11/96119266 165 200815533 [Chem.146] OZ1 (l-2a) In the formula (l-2a), the ring G1 may have a substituent in addition to -0Z1; Z1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent or may have a substituent In the formula (l-2b), the ring G2 may have a substituent in addition to -NZ2Z3; and Z2 and Z3 each independently represent a hydrogen atom, and a carbon group having a substituent of 1-4. Or a phenyl group which may have a substituent; [Chem. 148] Or may have a formula (l-2c), Z5 and Z7 independently represent a hydrogen atom 312XP / invention specification (supplement) / 96-11/96119266 166 200815533 base carbon number of 1 to 6; Z6 represents a hydrogen atom, a &gt;6 xanthate group, a cyano group, an amine oxime group, a thiol group, a sulfonate fluorenyl group or a carboxymethyl group; (l-2d) In the formula (l-2d), Z8 represents a methyl group, a carboxyl group or an alkoxycarbonyl group having 2 to 4 carbon atoms; and Z9 and Z1G each independently represent a hydrogen atom or a sulfonic acid group; a di-, non-hydrogen atom or a carbon group having a substituent of 1 to 6 carbon atoms, Z represents a hydrogen atom or a sulfonic acid group; [Chem. 151] ^ 312XP / invention specification (supplement) / 96-11/96119266 167 200815533 2f) wherein Z and z14 each independently represent a hydrogen atom, a halogen atom, a fluorenyl group, a thiol group, a carbon group having 1 to 4 carbon atoms which may have a substituent, and a calcination number of 1 to 4 which may have a substituent. a group or an acid group having a substituent of a carbon group of 1 to 7; [Chem. 152] (i) In the old secret formula (1 2g), 'Z and the shoulders respectively indicate that they may have a substituent; the alkyl group of 1 to 6; Qi represents an oxygen atom or a sulfur atom; 2. Table or NH group. Patent No. 1 of the first blind spear, which is an arsenazo pigment for an anisotropic pigment film, wherein the above formula (1) is represented by the following formula (1-3). [Chem. 153] A41 - 〆 (4) 312XP/Invention Manual (Supplement)/96-11/96119266 168 200815533 In the formula (1-3), A41 and A42 each independently represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent; X42 represents -CH2- group or -C0- group; R to R each independently represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group or a mercaptoamine group; Y2 and Y3 each independently represent a hydrogen atom, a methyl group or an ethyl group. 5. The azochrome for an anisotropic pigment film according to the ninth aspect of the patent application, wherein the above formula (1) is represented by the following formula (1 - 4). In the formula (1-4), A51 and A52 each independently represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent; and R51 and R52 each independently represent a hydrogen atom, a hydroxyl group, a dentate atom, a sulfonic acid group, or a carboxyl group; An alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an amine group which may have a substituent. 6. An azo dye for an anisotropic pigment film, characterized in that the free acid form is represented by the following formula (2): [Chem. 155] 312 χ ρ / invention specification (supplement) / 96-11/96119266 169 (2 ) 200815533 In the formula (2), 'A3' represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an aromatic heterocyclic group which may have a substituent or a group represented by the following formula (1 - /3); -CH2- group or -C0- group; _ γ6 represents a hydrogen atom, a fluorenyl group or an ethyl group; and R13 to R15 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and may have a substituent of an amine group, a sulfonic acid group, a hydroxyl group, a nitro group or a carboxyl group, wherein Ar represents a 1,4-extension base, a 1,4-naphthyl group, a 1, a naphthyl group, a 2-nene group or a formula a group represented by (l-a2); 1,4 - phenylphenone, 1,4-naphthyl, 1,5-naphthyl, 2,6-anthranyl, and by the following formula (I-") The base of the representation 'may also have a substituent; _ [Chem. 156] (1) In the formula (ΐγ), Q and Q each independently represent an oxygen atom or an NH group; ... independently represent a hydrogen atom, an alkyl group which may have a substituent, or an amine group which may have a substituent; Combining to form a ring; 312XP/invention specification (supplement)/96-11/96119266 170 200815533 [Chem. 157] In the formula (1-a2), silver/5 is a heterocyclic ring of 5 or 6 membered rings. 7. The azochrome for anisotropic pigment enamel according to item 6 of the patent application, wherein the above formula (2) is represented by the following formula (2-1): • [Chem. 158] In the formula (2-1), A63 represents a phenyl group having, as a substituent, one or two groups selected from the group consisting of a sulfonic acid group and a group having a substituent and an alkoxy group which may have a substituent. And the R. An atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amine group which may have a substituent, a carboxyl group or a sulfonic acid group; R represents a hydrogen atom, a nitro group, an alkoxy group which may have a substituent, The amine group which may have a substituent may be used as a base or 312XP/invention specification (supplement)/96q 1/961丨9266 171 200815533. 8. The anisotropic substance 'where' is expressed by the following formula (2-2) by the following formula (2-2) using an azo color [Chem. 159] * (2,2) represents a phenyl group which may have a substituent or may have a naphthyl group which is a substituent of the formula (2-2); and R73 and R74 each independently represent a hydrogen atom, a succinct, a sucrose group, or a s The base of the group, the alkoxy group which may have a substituent, the amine group or the imide amines X7 and Y6 are respectively synonymous with the above formula (2). 312XP/Invention Manual (supplement)/96-11/96119266 172