JP2009263514A - Water-soluble azo compound or its salt, ink composition and colored material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye having a high color intensity suitable for ink-jet recording and excellent ink composition storage stability and an ink composition containing the same. <P>SOLUTION: The water-soluble azo compound is represented by formula (1) [wherein R is a 1-4C alkoxy group or the like; n is 1 or 2; m is 1-3; x is an integer of 2-4 or the like; group A is a hydroxy-substituted mono 1-4C aliphatic amino group, a carboxy-substituted 1-20C aliphatic amino group, an unsubstituted five- or six-membered nitrogen-containing heterocyclic group, a substituted aromatic amino group or the like; the aromatic ring containing a ring represented by a broken line is a benzene ring when a ring represented by a broken line does not exist and is a naphthalene ring when a ring represented by a broken line exists] or its salt. The ink composition suitable for ink-jet recording contains the compound as a dye. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a water-soluble azo compound or a salt thereof, an ink composition containing the same, and a colored product colored with the ink composition.

Among various color recording methods, various ink ejection methods have been developed as recording methods using an ink jet printer, which is one of the representative methods. All of these generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. This method has been rapidly spreading in recent years due to the features that the recording head and the recording material are not in direct contact, so there is no sound generation and is quiet, and the size, speed, and color are easy. Large growth is expected in the future. Conventionally, inks such as fountain pens and felt pens and inks for ink jet recording have been used inks in which a water-soluble dye is dissolved in an aqueous medium. In order to prevent clogging, a water-soluble organic solvent is generally added. These inks provide a recording image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Is required. The formed recorded image is required to have fastness such as water resistance, moisture resistance, light resistance, and gas resistance.
Ink jet printer nozzle clogging occurs when the water content in the ink evaporates in the vicinity of the nozzle before other solvents and additives, and the pigment solidifies and precipitates when the composition state is low in water and high in solvents and additives. There are many things that come from doing. Therefore, one of the very important required performances is that solids are difficult to deposit even when the ink is evaporated and dried. For this reason, high solubility in solvents and additives is one of the properties required for pigments.

  By the way, in order to record image or character information on a color display of a computer in color by an ink jet printer, generally four colors represented by yellow (Y), magenta (M), cyan (C) and black (K) are used. Subtractive color mixing with ink is used, whereby the recorded image is expressed in color. In order to reproduce the additive color mixture image of red (R), green (G), and blue (B) on a CRT (CRT) display etc. as faithfully as possible with the subtractive color mixture image, each dye used in the ink, especially Y, It is desired that each of M and C has a hue close to a standard and is clear. In addition, the ink is stable for long-term storage, has a high density of the printed image as described above, and has excellent fastness such as water resistance, moisture resistance, light resistance and gas resistance. Desired. Here, the gas resistance refers to a phenomenon in which a gas having an oxidizing action present in the air reacts with a dye (dye) of a recorded image on the recording paper or in the recording paper to cause the printed image to discolor. It is resistance. Among the oxidizing gases, ozone gas is considered to be a main causative substance that promotes the fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet images, improvement of ozone gas resistance is an important technical problem in this field.

In order to obtain photographic image quality, an ink receiving layer may be provided on the surface of an ink jet dedicated paper which is one of recording papers. This ink-receiving layer is often made of a porous white inorganic material in order to expedite ink drying and to reduce bleeding at high image quality. In particular, on such recording paper, discoloration due to ozone gas occurs. It is noticeable. With the recent spread of digital cameras and color printers, there are increasing opportunities to print images obtained with digital cameras etc. as photographic image quality at home, and when storing the obtained prints, these oxidizing gases in the air In many cases, the discoloration of the image due to the ozone gas resistance is regarded as a problem.
Here, as for the yellow color, a dye and an ink having better resistance to an oxidizing gas have been developed and used compared to magenta and cyan, which are other basic colors of subtractive color mixing. Of the various fastnesses mentioned above, water resistance and moisture resistance are required characteristics that are relatively easy to improve fastness by improving the recording material. Therefore, among the fastness required for yellow dyes for ink jet and yellow ink, the most desired improvement is often the light resistance of the recorded image.

Examples of yellow pigments for inkjet which have excellent water solubility and sharpness and have been conventionally used include C.I. I. (Color index) Direct yellow 132 is mentioned, and its use examples are disclosed in Patent Documents 1 to 3.
Further, Patent Document 4 discloses a highly fast azo yellow dye for ink jet recording.

JP-A-11-70729 JP2000-154344, Examples A1-5 JP-A-2003-34763, page 24, Table 1-1, Example 4 JP 2006-152244 A

C. I. Direct Yellow 132 does not have sufficient performance in all of various fastnesses such as hue, sharpness, and light resistance, and storage stability. The yellow pigment described in Patent Document 4 has various fastnesses such as light resistance at a very high level, but has a problem that the color density is slightly insufficient. There was a problem that the concentration of the dye inside had to be increased. Increasing the concentration of the dye in the ink not only increases the cost of the ink, but also increases the possibility that the dye will precipitate as a solid, which can easily cause problems such as nozzle blockage in the inkjet printer. Color density is one of the very important physical properties. Accordingly, there has been a demand for the development of yellow pigments that are further improved in terms of fastness and color density, as well as hue and vividness, and in particular, pigments that have an excellent balance between fastness and color density. In other words, in the case of a dye having a low color density but excellent in various fastness properties, it is necessary to increase the dye content in the ink for balance with other colors. Here, since the coloring matter is usually solid, problems such as storage stability of the ink due to precipitation of solid content and ejection failure due to blockage of the nozzle opening of the ink jet printer due to an increase in coloring matter content Is likely to occur. Furthermore, an increase in the pigment content leads to an increase in the cost of the ink, which is disadvantageous economically. On the other hand, there is an advantage that the higher the color density of the pigment, the lower the pigment content in the ink. However, the lower the pigment content, the more the fastness of the pigment needs to be improved. For this reason, as a yellow dye for ink-jet recording, it is strongly desired to develop a dye having an excellent balance of a plurality of required physical properties rather than specializing in one physical property.
The present invention is highly soluble in water, has a hue and sharpness suitable for ink jet recording, has a high color density, and various fastnesses such as water resistance and moisture resistance of the recorded matter, particularly gas resistance and light resistance. An object of the present invention is to provide a water-soluble yellow pigment (compound) excellent in color density balance and an ink composition containing the same and having good storage stability.

As a result of intensive studies, the present inventors have solved the above-mentioned problems by a specific water-soluble disazo compound represented by the following formula (1) and an ink composition containing the same. And the present invention has been completed.
That is, the present invention is 1)
A water-soluble azo compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
R represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a sulfo group,
n represents 1 or 2, m represents an integer of 1 to 3, and x represents an integer of 2 to 4,
Group A includes a substituted or unsubstituted C1-C20 aliphatic amino group; a hydroxy-substituted mono- or di-C1-C4 aliphatic amino group; a carboxy-substituted C1-C20 aliphatic amino group; a substituted or unsubstituted 5- or 6-membered group. A nitrogen heterocyclic group; a substituted or unsubstituted aromatic amino group; or a substituted or unsubstituted aryl C1-C4 alkylamino group;
The aromatic ring substituted by the sulfo group represented by — (SO ₃ H) m is a benzene ring when a ring represented by a broken line is not present, and a naphthalene ring when a ring represented by a broken line is present. Respectively. ],
2)
Group A is a hydroxy-substituted mono- or di-C1-C4 aliphatic amino group; a carboxy-substituted C1-C20 aliphatic amino group; an unsubstituted 5- or 6-membered nitrogen-containing heterocyclic group; an aromatic group substituted with a sulfo group or a carboxy group A water-soluble azo compound or a salt thereof according to 1) above, which is an amino group; or a sulfo-substituted or unsubstituted phenyl C1-C4 alkylamino group;
3)
The water-soluble azo compound or a salt thereof according to 1) or 2) above, wherein the 5- or 6-membered nitrogen-containing heterocyclic group is a piperidinyl group or a morpholinyl group,
4)
The water-soluble azo compound or a salt thereof according to any one of 1) to 3) represented by the following formula (2):

[In Formula (2), q represents the integer of 1 or 2, and R, n, x, and group A represent the same meaning as in Formula (1). ].
5)
The water-soluble azo compound according to any one of 1) to 3) above, wherein the group A is a group selected from the group consisting of a morpholinyl group and an amino group represented by the following formulas (3) to (6): Or its salt,

[In Formula (3), y represents an integer of 1 to 11. ]

[In Formula (4), z represents an integer of 1 to 3, and k represents an integer of 0 to 2, respectively. ]

6)
R is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a sulfo group,
n represents 1 or 2, q represents 1, and x represents an integer of 2 to 4, respectively.
Group A is a morpholinyl group; formula (3) and y is an integer from 5 to 11; formula (4) and z is from 1 to 3, and k is from 0 to 2; formula (5) And the substitution position of the sulfo group whose substitution position is not specified is the 3-position or the 4-position when the substitution position of the amino group is the 1-position; The water-soluble azo compound or a salt thereof according to 4) or 5) above, wherein the substitution position of the group is the 3-position or 4-position when the substitution position of the amino group is the 1-position;
7)
R is a C1-C4 alkoxy group,
n represents 1, q represents 1, and x represents an integer of 2 to 4, respectively.
Group A is a morpholinyl group; formula (3) and y is an integer from 5 to 8; formula (4) and z is 1, and k is 1; formula (5) and the substitution position When the substitution position of the unspecified sulfo group is the 3-position when the substitution position of the amino group is the first position; the substitution position of the carboxy group of formula (6) and the substitution position of which is not specified is amino The water-soluble azo compound or a salt thereof according to any one of 4) to 6) above, which is the 3-position when the substitution position of the group is the 1-position;
8)
An ink composition containing the water-soluble azo compound or a salt thereof according to any one of 1) to 7) as a pigment;
9)
The ink composition as described in 8) above, further containing a water-soluble organic solvent,
10)
The ink composition as described in 8) or 9) above, which is for inkjet recording,
11)
The ink composition according to any one of the above 8) to 10) is used as an ink, and ink jet recording is performed on a recording material by ejecting ink droplets of the ink composition according to a recording signal. Recording method,
12)
The inkjet recording method according to 11) above, wherein the recording material is an information transmission sheet,
13)
The inkjet recording method according to 12) above, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance,
14)
A colored body colored with the water-soluble azo compound or salt thereof according to any one of 1) to 7), or the ink composition according to any one of 8) to 10);
15)
The colored body as described in 14) above, wherein coloring is performed by an ink jet printer,
16)
An inkjet printer loaded with a container containing the ink composition according to any one of 8) to 10) above;
About.

  The water-soluble azo compound represented by the above formula (1) of the present invention or a salt thereof is extremely excellent in solubility in water as compared with conventional products. In addition, it has a feature of good filterability, for example, for a membrane filter in the process of producing an ink composition, and gives a very clear yellow hue with high brightness and color density on inkjet recording paper. Further, the ink composition of the present invention containing this compound does not cause solid precipitation, changes in physical properties, changes in hue, etc. after long-term storage, and has extremely good storage stability compared to conventional products. A printed matter using the ink composition of the present invention as an ink for ink-jet recording has an ideal hue as a yellow hue without selecting a recording material (for example, paper, film, etc.). It is also possible to reproduce it faithfully on paper. Furthermore, even when recording on a recording material coated with a porous white inorganic material such as paper for exclusive use for photographic image quality and film, various fastnesses, that is, various fastnesses such as water resistance and moisture resistance, especially gas resistance In addition, the light resistance is good, and the long-term storage stability of a photographic-tone recorded image is excellent. As described above, the water-soluble azo compound represented by the formula (1) is extremely useful as a yellow coloring matter for ink, particularly for ink for inkjet recording.

The present invention will be described in detail. In the present specification, unless otherwise specified, acidic functional groups such as sulfo group and carboxy group are represented in the form of free acid.
In the following description, unless otherwise specified, “the water-soluble azo compound of the present invention or a salt thereof” is simply described as “the water-soluble azo compound of the present invention” for convenience.
The water-soluble azo compound of the present invention represented by the above formula (1) is a yellow dye useful for various recordings, particularly for ink jet recording, and the ink composition of the present invention containing the dye is used for ink jet recording. It is suitable as a yellow ink for use.

In the above formula (1), R represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a sulfo group, n is 1 or 2, m is 1 to 3, and x is an integer of 2 to 4. Each group A represents a substituted or unsubstituted C1-C20 aliphatic amino group; a hydroxy-substituted mono- or di-C1-C4 aliphatic amino group; a carboxy-substituted C1-C20 aliphatic amino group; a substituted or unsubstituted 5 or A 6-membered nitrogen-containing heterocyclic group; a substituted or unsubstituted aromatic amino group; or a substituted or unsubstituted aryl C1-C4 alkylamino group, substituted with a sulfo group represented by — (SO ₃ H) m The aromatic ring to be represented represents a benzene ring when there is no ring represented by a broken line, and represents a naphthalene ring when a ring represented by a broken line is present.

The C1-C4 alkyl group for R may be either a straight chain or a branched chain, but is preferably a straight chain. Specific examples include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, 1-methylpropyl and t-butyl.
The C1-C4 alkoxy group for R may be either linear or branched, but is preferably linear. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; branched chain such as isopropoxy, isobutoxy, 1-methylpropoxy and t-butoxy.
R is preferably a hydrogen atom, methyl or methoxy, and more preferably methoxy.
The substitution position of R is not particularly limited. However, when the substitution position of the amino group bonded to the triazine ring is 1-position, it is 2-position or 3-position, and 2-position is preferred.

M in the above formula (1) is 1 to 3, preferably 1.
Similarly, n is 1 or 2, preferably 1.
Similarly, x is 2 to 4, preferably 3.

In the above formula (1), the group A is a substituted or unsubstituted C1-C20 aliphatic amino group; a hydroxy-substituted mono- or di-C1-C4 aliphatic amino group; a carboxy-substituted C1-C20 aliphatic amino group; A substituted 5- or 6-membered nitrogen-containing heterocyclic group; a substituted or unsubstituted aromatic amino group; or a substituted or unsubstituted aryl C1-C4 alkylamino group.
The substituted or unsubstituted C1-C20 aliphatic amino group in the group A may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The substituent is not particularly limited, and preferred examples include an oxo group and a C1-C4 alkoxy group. Specific examples thereof include methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, tridecylamino, tetradecylamino, penta Unsubstituted straight chain such as decylamino, hexadecylamino, heptadecylamino, octadecylamino, nonadecylamino and eicosanylamino; oxo-substituted such as n-propionylamino and isopropionylamino; methoxyethylamino, ethoxyethyl C1-C4 alkoxy-substituted ones such as amino;
Examples of the hydroxy-substituted mono- or di-C1-C4 aliphatic amino group in group A include hydroxy-substituted mono C1-C4 alkylamino groups such as hydroxyethylamino; hydroxy-substituted diC1-C4 alkylamino groups such as bis- (hydroxyethyl) amino Group; etc. are mentioned.
The carboxy-substituted C1-C20 aliphatic amino group in the group A may be either linear or branched, but is preferably a linear one. Of these, a carboxy-substituted C1-C20 alkylamino group is preferable. The range of the carbon number is usually C1-C20, preferably C1-C11, more preferably C5-C11, and still more preferably C5-C8. Specific examples include carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, carboxy-n-pentylamino, carboxy-n-hexylamino, carboxy-n-heptylamino, carboxy-n-octyl. Amino, carboxy-n-nonylamino, carboxy-n-decanylamino, carboxy-n-undecanylamino, carboxy-n-dodecanylamino, carboxy-n-tridecanylamino, carboxy-n-tetradecanylamino, carboxy -N-pentadecanylamino, carboxy-n-hexadecanylamino, carboxy-n-heptadecanylamino, carboxy-n-octadecanylamino, carboxy-n-nonadecanylamino, carboxy-n-eicosa A carboxy-substituted mono C1-C20 alkylamino group such as ruamino; a carboxy-substituted diC1-C20 alkylamino group such as bis- (carboxymethyl) amino, bis- (carboxyethyl) amino, bis- (carboxypropyl) amino, etc. .
Examples of the substituted or unsubstituted 5- or 6-membered nitrogen-containing heterocyclic group in the group A include those containing 0 or 1 oxygen atom. Specific examples include pyrrolidinyl, piperidinyl, morpholinyl and the like, preferably piperidinyl or morpholinyl, more preferably morpholinyl. These may have a substituent, but are preferably unsubstituted.
Examples of the substituted or unsubstituted aromatic amino group in the group A include a substituted or unsubstituted phenylamino group or naphthylamino group, and the former is preferable. Although it does not restrict | limit especially as a substituent of this aromatic amino group, The 1 or 2 substituent selected from the group which consists of sulfo, carboxy, C1-C4 alkoxy, and hydroxy is mentioned, Sulfo or carboxy is preferable. The number of substituents is preferably 1. Specific examples include unsubstituted phenylamino; sulfo-substituted ones such as 2-, 3-, or 4-sulfophenylamino; 2-, 3-, or 4-carboxyphenylamino, 3,5-biscarboxyphenylamino Carboxy-substituted ones such as 3- or 4-methoxyphenylamino; hydroxy-substituted ones such as 2-, 3-, or 4-hydroxyphenylamino; 3-carboxy-4-hydroxyphenyl Carboxy and hydroxy substituted such as amino; carboxy and sulfo substituted such as 2-carboxy-4-sulfophenylamino; and the like.
Examples of the substituted or unsubstituted aryl C1-C4 alkylamino group in the group A include a substituted or unsubstituted phenyl C1-C4 alkylamino group or a naphthyl C1-C4 alkylamino group, and the former is preferable. Although it does not restrict | limit especially as this substituent, A sulfo is preferable and the phenyl group which the sulfo group substituted 1 or 2 on the benzene ring is more preferable. Specific examples thereof include unsubstituted ones such as benzylamino and phenethylamino; (4-sulfophenyl) methylamino, (4-sulfophenyl) ethylamino, (2,4-disulfophenyl) ethylamino, And the like in which the sulfo group is substituted on the benzene ring 1 or 2;

The aromatic ring substituted by the sulfo group represented by — (SO ₃ H) m is a benzene ring when a ring represented by a broken line is not present, and a naphthalene ring when a ring represented by a broken line is present. Represents. The ring represented by the broken line may be present but is preferably absent.

  The group A includes a hydroxy-substituted mono- or di-C1-C4 aliphatic amino group; a carboxy-substituted C1-C20 aliphatic amino group; an unsubstituted 5- or 6-membered nitrogen-containing heterocyclic group; an aromatic group substituted with a sulfo group or a carboxy group Group amino group; or sulfo-substituted or unsubstituted phenyl C1-C4 alkylamino group; Specific examples thereof are as described above.

  A more preferable compound represented by the above formula (1) is a compound represented by the above formula (2).

In the above formula (2), q represents an integer of 1 or 2, and R, n, x and group A represent the same meaning as in the above formula (1), and preferred examples thereof are also preferred. And the same as in the above formula (1). q is usually 1 or 2, preferably 1.

A more preferable compound in the above formula (2) is a compound in which the group A is a group selected from the group consisting of a morpholinyl group; and an amino group represented by the above formulas (3) to (6).
In the above formula (3), y is 1 to 11, preferably 5 to 11, more preferably 5 to 8, and particularly preferably 5.
In the above formula (4), k is 0 to 2, preferably 1, and z is 1 to 3, preferably 1. When k in Formula (4) is other than 0, that is, when the sulfo group has an unspecified substitution position, the substitution position of the sulfo group is not particularly limited, but the substitution position of the alkylene group is the 1st position In addition, the 2-position and / or the 4-position is preferable, and the 4-position is more preferable.

  As one of the preferable combinations in the above formula (2), R is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a sulfo group, n is 1 or 2, q is 1, and x is 2 Each represents an integer from 1 to 4, the group A is a morpholinyl group; formula (3), and y is an integer from 5 to 11; formula (4), and z is from 1 to 3, and k is from 0 2; in the formula (5), the substitution position of the sulfo group whose substitution position is not specified is the 3rd or 4th position when the substitution position of the amino group is the 1st position; the formula (6), and The substitution position of the carboxy group whose substitution position is not specified is the 3rd or 4th position when the substitution position of the amino group is the 1st position. One of the more preferred combinations is that R is a C1-C4 alkoxy group, n is 1, q is 1, and x is an integer of 2 to 4, respectively, and the group A is a morpholinyl group; 3) and y is an integer of 5 to 8; the formula (4) and z is 1, and k is 1; the substitution of the sulfo group whose formula is (5) and whose substitution position is not specified The position is the 3rd position when the substitution position of the amino group is the 1st position; the substitution position of the carboxy group which is the formula (6) and the substitution position is not specified, the substitution position of the amino group is the 1st position In some cases;

In the above formulas (1) to (6), compounds in which preferable ones are combined with each other with respect to R, n, m, x, groups A, q, y, z and k and their substitution positions are more preferable and more preferable. What combined each other is still more preferable. The same applies to preferable ones. The same applies to preferred combinations and preferred combinations.

  The compound represented by the above formula (1) exists also as a free acid or a salt thereof. Examples of the salt of the compound represented by the above formula (1) include salts with inorganic or organic cations. Specific examples of the inorganic cation salt include alkali metal salts such as lithium, sodium, potassium and the like. Examples of the organic cation include, but are not limited to, quaternary ammonium salts represented by the following formula (7).

Wherein (7), represents the Z ¹ to Z ⁴ each independently represent a hydrogen atom, a C1-C4 alkyl group, hydroxy C1-C4 alkyl group or a hydroxy C1-C4 alkoxy C1-C4 alkyl group. ]

Here, examples of the alkyl group in Z ^{1 to} Z ⁴ include methyl, ethyl and the like, and examples of the hydroxyalkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxy Examples of the hydroxyalkoxyalkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, and 3- (hydroxyethoxy). Examples include butyl and 2- (hydroxyethoxy) butyl.

  Preferable examples of the salt include sodium, potassium, lithium, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine salt, and ammonium salt. Of these, lithium, sodium, and ammonium salts are particularly preferred.

The yellow pigment | dye represented by the said Formula (1) of this invention can be manufactured as follows, for example. In addition, R, m, n, and x which are appropriately used in the following formulas (A) to (I) represent the same meaning as in the above formula (1).
The compound represented by the following formula (A) obtained by referring to the example described in JP-A-2004-75719 is changed to a methyl-ω-sulfonic acid derivative (B) using sodium bisulfite and formalin. Subsequently, the aminobenzenesulfonic acid represented by the following formula (C) is diazotized by a conventional method, and the methyl-ω-sulfonic acid derivative represented by the formula (B) obtained above and 0 to 15 ° C., pH 2 A compound represented by the following formula (D) is obtained by performing a coupling reaction at ˜4, and subsequently carrying out a hydrolysis reaction at 80 to 95 ° C. and pH 10.5 to 11.5.

  Further, a compound represented by the following formula (E) is used instead of the compound represented by the above formula (A), and a compound represented by the following formula (F) is used instead of the compound represented by (C). Except for the above, a compound represented by the following formula (G) is obtained by the same method as described above.

  Next, the compound represented by the above formula (G) (1 equivalent) and cyanuric halide (1 equivalent), for example, cyanuric chloride, are condensed at a temperature of 0 to 15 ° C. and slightly acidic (usually pH 5 to 6). By doing this, a compound represented by the following formula (H) is obtained. Subsequently, the compound represented by the formula (D) (1 equivalent) and the compound represented by the formula (H) (1 equivalent) are condensed at a temperature of 20 to 35 ° C. and slightly acidic (usually pH 6 to 7). Thus, a compound represented by the following formula (I) is obtained.

  Furthermore, the chlorine atom in the obtained compound represented by the formula (I) is preferably an aliphatic or aromatic amine which may have a substituent under the conditions of 80 to 95 ° C. and pH 7 to 9. By substituting, the dye of the present invention represented by the above formula (1) can be obtained.

Specific examples of the compound represented by the formula (A) include 2- (sulfoethoxy) aniline, 2- (sulfopropoxy) aniline, and 2- (sulfobutoxy) aniline, which are represented by the formula (C). Examples of the compound to be produced include 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 4-aminobenzene-1,3-disulfonic acid, and 2-aminobenzene-1,4- Specific examples include disulfonic acid.
Specific examples of the compound represented by the above formula (E) include aniline, 3-methylaniline, 2-methylaniline, 2-methoxyaniline, 3-methoxyaniline, and the like. As the compound represented by the formula, 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-5,7- Specific examples include disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, and 2-aminonaphthalene-4,6,8-trisulfonic acid.

Next, preferred specific examples of the dye of the present invention are shown in Table 1 below. In Table 1, the sulfo group is represented in the form of the free acid.

As will be apparent to those skilled in the art, the salt of the compound represented by the above formula (1) can be easily obtained by the following method.
For example, the reaction solution before adding 800 parts of acetone in Example 1 described later, or an aqueous solution in which a wet cake containing a compound represented by the formula (1) or a dried product of the compound represented by the formula (1) is dissolved. Sodium chloride is added to and salted out, and the precipitated solid is collected by filtration, whereby the sodium salt of the compound represented by the above formula (1) can be obtained as a wet cake.
Further, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is collected by filtration. By washing with acidic water, inorganic salts contained as impurities, such as sodium chloride and sodium sulfate, can be removed, and the free acid of the compound represented by the above formula (1) or the formula (1) It is also possible to obtain a mixture of a free acid and a sodium salt, part of which is a sodium salt.
Furthermore, while stirring the wet cake of the free acid of the compound represented by the formula (1) with water, for example, an inorganic base such as potassium hydroxide, lithium hydroxide, aqueous ammonia, or the above formula (7) If an organic base such as a hydroxide of a compound is added to make it alkaline, a corresponding potassium salt, lithium salt, ammonium salt, or quaternary ammonium salt can be obtained. By limiting the number of moles of the above-mentioned salt to the number of moles of free acid, it is possible to prepare, for example, a mixed salt of lithium and sodium, and further a mixed salt of lithium, sodium, and ammonium. is there.
Inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, and ammonium hydroxide. (Ammonia water) or the like is used.
Examples of the organic base include, for example, a quaternary ammonium salt represented by the formula (7), such as a salt of alkanolamine such as diethanolamine and triethanolamine, but is not limited thereto.
The salt of the compound represented by the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the target ink performance.

The coloring matter of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and also for producing writing ink and ink composition for ink jet recording.
The reaction solution of the final step in the synthesis reaction of the water-soluble azo compound of the present invention can be directly used for the production of the ink composition of the present invention. However, the compound can be isolated from the reaction solution by, for example, crystallization or spray drying, and then dried as necessary, and an ink composition can be prepared using the obtained compound. In the ink composition of the present invention, the water-soluble azo compound of the present invention is used as a pigment, and is usually 0.1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 2% in the total mass of the ink composition. Contains ~ 8% by mass.

  In the ink composition of the present invention, the compound represented by the formula (1) is dissolved in an aqueous medium such as water and / or a water-soluble organic solvent (an organic solvent miscible with water), and an ink is prepared as necessary. The agent is added. When this ink composition is used as an ink for an ink jet printer, it is preferable to use a metal cation chloride contained as an impurity, such as sodium chloride, sulfate, eg, an inorganic substance such as sodium sulfate. . In this case, for example, the total content of sodium chloride and sodium sulfate is about 1% by mass or less in the total amount of the water-soluble azo compound of the present invention. In order to produce the compound containing less inorganic impurities, for example, a method using a known reverse osmosis membrane or a dried product or wet cake of the compound of the present invention or a salt thereof is stirred in a mixed solvent of alcohol such as methanol and water. The suspension may be purified by suspension, and the solid may be filtered off and dried for desalting.

  The ink composition of the present invention is prepared using water as a medium, and may contain a water-soluble organic solvent as necessary within a range that does not impair the effects of the present invention. The water-soluble organic solvent may have a function equivalent to a dye solubilizer, a drying inhibitor (wetting agent), a viscosity modifier, a penetration accelerator, a surface tension modifier, an antifoaming agent, and the like. It is preferable to contain it in the product. Other ink regulators include, for example, antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, UV absorbers, viscosity modifiers, dye solubilizers, antifading agents, emulsion stabilizers, surface tension modifiers. , Known additives such as antifoaming agents, dispersants, and dispersion stabilizers. The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0 to 15% by mass, based on the entire ink. % Is good. The remainder other than the above is water.

  Examples of water-soluble organic solvents that can be used in the present invention include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; N, N-dimethyl Amides such as formamide or N, N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one Heterocyclic ketones such as: ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or keto alcohols; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2- or 1,3- Propylene glycol, 1,2- or 1, Mono, oligo or poly having C2-C6 alkylene units such as butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol or thiodiglycol Alkylene glycol or thioglycol; polyol (triol) such as glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbyl) Toll), triethylene glycol monomethyl ether, triethylene C1-C4 monoalkyl ether of polyhydric alcohol such as glycol monoethyl ether; gamma-butyrolactone or dimethyl sulfoxide and the like.

  Preferred as the above water-soluble organic solvent are isopropanol, glycerin, mono, di or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol, more preferably isopropanol, Glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol. These water-soluble organic solvents are used alone or in combination.

Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone System, benzyl bromacetate system.
Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide, and examples of the isothiazoline compound include 1,2-benzisothiazoline. -3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one Examples thereof include magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, and 2-methyl-4-isothiazolin-3-one calcium chloride.
Other antiseptic and antifungal agents include sodium acetate, sodium sorbate, sodium benzoate and the like. In addition, specific examples of antiseptic / antifungal agents include, for example, trade names Proxel GXL (S) and Proxel XL-2 (S) manufactured by Avecia.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. And carbonates.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.

  Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the ultraviolet absorber include a compound that emits fluorescence by absorbing ultraviolet rays typified by benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, or benzoxazole compounds, so-called fluorescence. Brightening agents can also be used.

  Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

  Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like. It is preferred to use urea.

  The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles, and metal complexes include There are nickel complexes and zinc complexes.

  Examples of the surface tension adjusting agent include surfactants, and examples include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.

  Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl allyl sulfonate, diethyl sulfosuccinate , Diethylhexylsyl sulfosuccinate, dioctyl sulfosuccinate and the like.

  Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. There is.

  Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ethers; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene Esters such as stearates; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl- -Acetylene glycol (alcohol) series such as octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, and other specific examples, for example, trade name Surfynol 104, 82 manufactured by Nisshin Chemical Co., Ltd. 465, Olfin STG and the like.

  As the antifoaming agent, a highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, or silicone-based compound is used as necessary.

  These ink preparation agents are used alone or in combination. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m. The viscosity of the ink composition of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.

  In order to produce the ink composition of the present invention, there is no particular limitation on the order of dissolving each agent such as an additive. In preparing the composition, water to be used is preferably one having few impurities such as ion exchange water or distilled water. Furthermore, if necessary, fine filtration may be performed using a membrane filter to remove impurities. When used as ink for an inkjet printer, it is preferable to perform fine filtration. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 microns, preferably 0.8 to 0.2 microns.

  The ink composition containing the water-soluble azo compound of the present invention is suitable for use in printing, copying, marking, writing, drawing, stamping, or recording (printing), particularly in inkjet recording. In addition, the ink composition of the present invention hardly causes crystal precipitation even when dried in the vicinity of the nozzles of the ink jet printer, and for this reason, the head is not easily blocked. Further, when the ink composition of the present invention is used for ink jet recording, a yellow print with high quality and particularly high color density having good resistance to water, light, ozone and friction can be obtained.

  In some inkjet printers, two types of ink, high density ink and low density ink, are loaded in one printer for the purpose of supplying a high-definition image. In that case, a high-concentration ink composition and a low-concentration ink composition may be produced using the water-soluble azo compound of the present invention, and these may be used as an ink set. Moreover, you may use this compound only for either one. Moreover, you may use together the water-soluble azo compound of this invention, and a well-known yellow pigment | dye. In addition, the colorant of the present invention can be used for toning of other colors, for example, black ink, or for the purpose of preparing a red ink or a green ink by mixing with a magenta colorant or a cyan colorant.

  The colored product of the present invention is a substance colored with the water-soluble azo compound of the present invention or an ink composition containing the compound of the present invention. The material of the colored body is not particularly limited. For example, a sheet for information transmission such as paper or film, fiber or cloth (cellulose, nylon, wool, etc.), leather, a base material for a color filter, or the like may be used. Anything is acceptable and not limited to these. Examples of the coloring method include a printing method such as dip dyeing, textile printing, and screen printing, an ink jet recording method using an ink jet printer, and the method using ink jet recording is preferable.

The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; or inorganic fine particles capable of absorbing a pigment in ink such as porous silica, alumina sol, and special ceramics such as polyvinyl alcohol and polyvinyl pyrrolidone. A method of coating the surface of the base material together with a hydrophilic polymer.
Those provided with such an ink receiving layer are usually called ink jet exclusive paper, ink jet exclusive film, glossy paper, or glossy film.
Among these, the porous silica, alumina sol, special ceramics, etc. mentioned above are coated on the substrate surface because they are easily affected by gases having an oxidizing action in the air, that is, ozone gas and nitrogen oxide gas. This is a special inkjet paper.
For example, typical commercially available paper for inkjet use includes Canon Inc., trade name Professional Photo Paper, Super Photo Paper, and Glossy Gold; Seiko Epson Corporation trade name Photo Paper Crispia (high Gloss), photo paper (gloss); Nippon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper (gloss); Fuji Film Co., Ltd.
Since the ink composition of the present invention is excellent in the resistance to the gas having the above oxidizing action, it provides an excellent recorded image with little discoloration even when recording on such a recording material. It can also be used for plain paper.

In order to record on a recording material by the ink jet recording method of the present invention, for example, a container filled with the ink composition described above is set at a predetermined position of an ink jet printer and recorded on the recording material by a normal method. Good. In the inkjet recording method of the present invention, a magenta ink, a cyan ink, and, if necessary, a green ink, a blue (or violet) ink, a red ink, and a black ink can be used in combination with the ink composition of the present invention. In this case, the inks of the respective colors are injected into the respective containers, and these containers are used in a predetermined position of the ink jet printer.
Some inkjet printers use, for example, a piezo method using mechanical vibration, a bubble jet (registered trademark) method using bubbles generated by heating, or the like. The ink jet recording method of the present invention can be used by any method.

The ink composition of the present invention has a clear yellow color, particularly high image clarity recorded on ink jet dedicated paper and glossy paper, and particularly high color density, and has a hue suitable for the ink jet recording method. Further, the recorded image is characterized by extremely high various fastnesses such as light resistance and ozone resistance.
The ink composition of the present invention does not precipitate or separate during storage, and has extremely high storage stability. Further, when the ink composition of the present invention is used for ink jet recording, crystal precipitation due to drying of the ink composition in the vicinity of the nozzle is very unlikely to occur, and the ejector (ink head) is not blocked. The ink composition of the present invention uses a continuous ink jet printer and has physical properties even when the ink is recirculated at relatively long time intervals or intermittently used by an on-demand ink jet printer. Does not change.

Hereinafter, the present invention will be described more specifically with reference to examples. In the text, “parts” and “%” are based on mass unless otherwise specified, and the reaction temperature is also the internal temperature. Operations such as each reaction and crystallization in the examples were carried out with stirring unless otherwise specified.
In addition, (lambda) max (maximum absorption wavelength) of each compound synthesize | combined showed the measured value in pH7-8 aqueous solution. The water-soluble azo compounds of the present invention obtained in the examples are all sodium salts, but for the sake of convenience, their chemical structural formulas are shown as free acids. However, as described above, a free acid or an alkali metal salt other than a sodium salt can be easily obtained by using an appropriate method, and the present invention is not limited to this example.

Example 1
(1)
17.3 parts of 3-aminobenzenesulfonic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 7.2 parts of sodium nitrite was added. This solution was added dropwise to 300 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out diazotization reaction to prepare a diazo reaction liquid.
On the other hand, 12.3 parts of 2-methoxyaniline is dissolved in 130 parts of water while adjusting the pH to 5 with sodium hydroxide, and is usually used with 10.4 parts of sodium bisulfite and 8.6 parts of 35% formalin. A methyl-ω-sulfonic acid derivative was obtained by the method.
The obtained methyl-ω-sulfonic acid derivative was added to the previously prepared diazo reaction solution, and the mixture was stirred at 0 to 15 ° C. and pH 2 to 4 for 5 hours. The reaction solution was adjusted to pH 11 with sodium hydroxide, stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH, further salted out by adding 100 parts of sodium chloride, and the precipitated solid was collected by filtration. 100 parts of an azo compound represented by the formula (10) was obtained as a wet cake.

(2)
17.3 parts of 3-aminobenzenesulfonic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 7.2 parts of sodium nitrite was added. This solution was added dropwise to 300 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out diazotization reaction to prepare a diazo reaction liquid.
Meanwhile, 23.1 parts of 2- (sulfopropoxy) aniline are dissolved in 130 parts of water while adjusting the pH to 7 with sodium hydroxide, and 10.4 parts of sodium bisulfite and 8.6 parts of 35% formalin are used. Thus, a methyl-ω-sulfonic acid derivative was obtained by a conventional method.
The obtained methyl-ω-sulfonic acid derivative was added to the previously prepared diazo reaction solution, and the mixture was stirred at 0 to 15 ° C. and pH 2 to 4 for 5 hours. The reaction solution was adjusted to pH 11 with sodium hydroxide, stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH, further salted out by adding 100 parts of sodium chloride, and the precipitated solid was collected by filtration. 130 parts of an azo compound represented by the formula (11) was obtained as a wet cake.

(3)
Lion Co., Ltd., trade name: Leocol TD90 (surfactant) 0.10 parts was added to 250 parts of ice water and stirred vigorously, and 8.0 parts of cyanuric chloride was added thereto, and 0 to 5 ° C. for 30 minutes. Stir to obtain a suspension.
A wet cake of 100 parts of the azo compound (10) obtained by the above method was dissolved in 200 parts of water, and the above suspension was added dropwise to this solution over 30 minutes. After completion of dropping, the mixture was stirred at pH 5-6 and 0-10 ° C. for 6 hours.
Next, a wet cake of 130 parts of the azo compound (11) obtained by the above method was dissolved in 300 parts of water and added dropwise to the above solution over 30 minutes. After completion of the dropwise addition, the mixture was stirred at pH 6-7 and 25-35 ° C. for 6 hours, 19.7 parts of 6-aminohexanoic acid was added, and the mixture was stirred at pH 7-9, 75-80 ° C. for 3 hours. After cooling the obtained reaction liquid to 20-25 degreeC, 800 parts of acetone was added to this reaction liquid, and it stirred at 20-25 degreeC for 1 hour. The precipitated solid was collected by filtration to obtain 95.0 parts of a wet cake. The wet cake was dried with a hot air dryer at 80 ° C. to obtain 30.0 parts of a water-soluble azo compound (λmax 394 nm) of the present invention represented by the following formula (12).

Example 2
In the same manner as in Example 1 except that 19.7 parts of 6-aminohexanoic acid used in Example 1 (3) was changed to 34.6 parts of 3-aminobenzenesulfonic acid, the formula (13) of the present invention was used. 15.0 parts of the water-soluble azo compound of the present invention (λmax 391 nm) was obtained.

Example 3
It is represented by the formula (14) of the present invention in the same manner as in Example 1 except that 19.7 parts of 6-aminohexanoic acid used in Example 1 (3) is changed to 27.4 parts of 3-aminobenzoic acid. 12.0 parts of the water-soluble azo compound of the present invention (λmax 393 nm) was obtained.

Example 4
In the same manner as in Example 1, except that 19.7 parts of 6-aminohexanoic acid used in Example 1 (3) was changed to 28.1 parts of 4- (aminomethyl) benzenesulfonic acid, the formula (15 29.0 parts of the water-soluble azo compound of the present invention (λmax 392 nm) represented by

Example 5
The method of the present invention represented by the formula (16) of the present invention is the same as in Example 1 except that 19.7 parts of 6-aminohexanoic acid used in Example 1 (3) is changed to 13.1 parts of morpholine. 27.5 parts of a water-soluble azo compound (λmax 401 nm) was obtained.

Example 6
The present invention represented by the formula (17) of the present invention in the same manner as in Example 1 except that 19.7 parts of 6-aminohexanoic acid used in Example 1 (3) was changed to 9.5 parts of ethanolamine. 27.0 parts of a water-soluble azo compound (λmax 396 nm) was obtained.

Examples 7-10
(A) Preparation of Ink The azo compounds of the present invention obtained in Examples 1 to 4 were used as dyes and mixed at the composition ratios shown in Table 2 below to obtain ink compositions of the present invention. A test ink was prepared by removing impurities by filtration through a 45 μm membrane filter. The water was ion-exchanged water, adjusted with an aqueous sodium hydroxide solution so that the pH of the ink composition was about 9, and water was added so that the total amount was 100 parts. Preparation of ink using the compound of Example 1 was performed in Example 7, and preparation of ink prepared using the compounds of Examples 2, 3, 4, 5 and 6 was similarly performed in Examples 8, 9, 10 and 6, respectively. 11 and 12.

Table 2 (Composition ratio of ink composition)
Azo compound obtained in each of the above Examples 3.5 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfynol 104PG50 (Note) 0.1 part Sodium hydroxide + water 77.4 parts Total 100.0 parts (Note) Acetylene glycol nonionic surfactant, manufactured by Nisshin Chemical Co., Ltd.

Comparative Example 1
Instead of the water-soluble azo compound of the present invention obtained in Examples 1 to 6, C.I. I. A comparative ink was prepared in the same manner as in each Example except that Direct Yellow 132 was used as a coloring matter. This is referred to as Comparative Example 1. The C.I. used in Comparative Example 1 was used. I. Since Direct Yellow 132 is commercially available in the form of an aqueous solution, the aqueous solution is obtained by drying at 60 ° C. for 2 weeks using a trade name Fine Oven DF42 manufactured by Yamato Scientific Co., Ltd. The compound was used.

Comparative Example 2
Instead of the water-soluble azo compound of the present invention obtained in Examples 1 to 6, each compound was used except that the compound represented by the following formula (18) synthesized by the method described in Example 1 of Patent Document 4 was used. Comparative inks were prepared in the same manner as in the examples. This is referred to as Comparative Example 2. In addition, evaluation was performed using the sodium salt of the compound represented by following formula (18).

(B) Inkjet printing Using an inkjet printer (trade name: PIXUS ip4100, manufactured by Canon Inc.), inkjet recording was performed on a dedicated inkjet paper (trade name: Professional Photo Paper PR-101 manufactured by Canon Inc.). During ink jet recording, an image pattern was created so that gradations with several levels of reflection density were obtained, and a yellow printed matter was obtained.
In the light resistance test and the ozone gas resistance test, the reflection density was measured for the portion where the reflection density D value of the printed matter before the test was closest to 1. The reflection density was measured using a color measurement system (SpectroEye, manufactured by GretagMacbeth) under the conditions of DIN, viewing angle 2 °, and light source D65 as the density reference.
Various test methods for recorded images and evaluation methods for test results are described below.

(C) Color density of printed matter Yellow density Dy value was measured using the said colorimetry system about the part with the highest reflection density among the images printed on the ink jet exclusive paper. This number should be large. The results are shown in Table 3.

(D) Xenon light resistance test A test piece printed on ink-jet paper is placed in a holder, and a xenon weatherometer XL75 (manufactured by Suga Test Instruments Co., Ltd.) is used. The temperature is 24 ° C, the humidity is 60% RH, Irradiated at 0.36 W / square meter illumination for 144 hours.
After the test, the reflection density was measured using a colorimetry system, and the residual ratio of the reflection density was calculated by (reflection density after test / reflection density before test) × 100 (%). The residual rate should be large.
The results are shown in Table 3.

(E) Ozone gas resistance test
The test piece printed on the inkjet paper is left for 8 hours in an environment of ozone concentration 10 ppm, humidity 60% RH, temperature 24 ° C. using an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.), and the reflection density is measured as described above. Color measurement was performed using a color system. After the measurement, the residual ratio of the dye was calculated by (reflected density after test / reflected density before test) × 100 (%). The residual rate should be large.
The results are shown in Table 3.

Table 3 Test results

(C) (D) (E)
Example 7 1.72 85 61
Example 8 1.74 85 63
Example 9 1.79 85 60
Example 10 1.77 85 60
Example 11 1.76 86 63
Example 12 1.79 87 60
Comparative Example 1 1.88 76 56
Comparative Example 2 1.65 93 75

As is clear from the results in Table 3, C.I. I. Comparative Example 1 using Direct Yellow 132 showed the highest color density among the tested inks, but the light resistance and ozone gas resistance, particularly ozone gas resistance, were extremely inferior compared to others. It was found that there was a problem with robustness.
On the other hand, Comparative Example 2 disclosed in Patent Document 4 as a high fastness yellow dye for ink jet recording showed the most excellent results in light resistance and ozone resistance, but the color density was extremely small compared to others. Value, and it was found that the color density was insufficient.
On the other hand, each example tends to be inferior to Comparative Example 2 in light resistance and in Comparative Example 1 in color density, but has a color density, light resistance and ozone resistance that are not found in each pigment of the Comparative Example. All were found to be well balanced pigments.

  From the above results, the water-soluble azo compound of the present invention is suitable for preparing inks for ink jet recording, and is excellent in various fastness properties, that is, light resistance, ozone gas resistance and the like, and has high water solubility. It is a well-balanced dye having a good hue and a high color density as yellow as well as being stable without causing precipitation or gelation even when stored for a long time. From these characteristics, it is clear that the azo compound of the present invention is a very useful compound as various dyes for recording ink, particularly as a yellow dye for inkjet ink.

Claims (16)

A water-soluble azo compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
R represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a sulfo group,
n represents 1 or 2, m represents an integer of 1 to 3, and x represents an integer of 2 to 4,
Group A includes a substituted or unsubstituted C1-C20 aliphatic amino group; a hydroxy-substituted mono- or di-C1-C4 aliphatic amino group; a carboxy-substituted C1-C20 aliphatic amino group; a substituted or unsubstituted 5- or 6-membered group. A nitrogen heterocyclic group; a substituted or unsubstituted aromatic amino group; or a substituted or unsubstituted aryl C1-C4 alkylamino group;
The aromatic ring substituted by the sulfo group represented by — (SO ₃ H) m is a benzene ring when a ring represented by a broken line is not present, and a naphthalene ring when a ring represented by a broken line is present. Respectively. ]. Group A is a hydroxy-substituted mono- or di-C1-C4 aliphatic amino group; a carboxy-substituted C1-C20 aliphatic amino group; an unsubstituted 5- or 6-membered nitrogen-containing heterocyclic group; an aromatic group substituted with a sulfo group or a carboxy group The water-soluble azo compound or a salt thereof according to claim 1, which is an amino group; or a sulfo-substituted or unsubstituted phenyl C1-C4 alkylamino group. The water-soluble azo compound or a salt thereof according to claim 1 or 2, wherein the 5- or 6-membered nitrogen-containing heterocyclic group is a piperidinyl group or a morpholinyl group. The water-soluble azo compound or a salt thereof according to any one of claims 1 to 3 represented by the following formula (2):

[In Formula (2), q represents the integer of 1 or 2, and R, n, x, and group A represent the same meaning as in Formula (1). ]. The water-soluble azo compound according to any one of claims 1 to 3, wherein the group A is a group selected from the group consisting of a morpholinyl group and an amino group represented by the following formulas (3) to (6). Its salt,

[In Formula (3), y represents an integer of 1 to 11. ]

[In Formula (4), z represents an integer of 1 to 3, and k represents an integer of 0 to 2, respectively. ]

R is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a sulfo group,
n represents 1 or 2, q represents 1, and x represents an integer of 2 to 4, respectively.
Group A is a morpholinyl group; formula (3) and y is an integer from 5 to 11; formula (4) and z is from 1 to 3, and k is from 0 to 2; formula (5) And the substitution position of the sulfo group whose substitution position is not specified is the 3-position or the 4-position when the substitution position of the amino group is the 1-position; or the formula (6) and the substitution position is specified. The water-soluble azo compound or a salt thereof according to claim 4 or 5, wherein the substitution position of the carboxy group is 3-position or 4-position when the substitution position of the amino group is 1-position. R is a C1-C4 alkoxy group,
n represents 1, q represents 1, and x represents an integer of 2 to 4, respectively.
Group A is a morpholinyl group; formula (3) and y is an integer from 5 to 8; formula (4) and z is 1, and k is 1; formula (5) and the substitution position The substitution position of the unspecified sulfo group is the 3-position when the substitution position of the amino group is the first position; or the substitution position of the carboxy group that is the formula (6) and the substitution position is not specified. The water-soluble azo compound or a salt thereof according to any one of claims 4 to 6, which is 3-position when the substitution position of the amino group is 1-position. An ink composition containing the water-soluble azo compound according to any one of claims 1 to 7 or a salt thereof as a coloring matter. The ink composition according to claim 8, further comprising a water-soluble organic solvent. The ink composition according to claim 8 or 9, which is for inkjet recording. Inkjet recording, wherein the ink composition according to any one of claims 8 to 10 is used as ink, and recording is performed on a recording material by ejecting ink droplets of the ink composition according to a recording signal. Method. The inkjet recording method according to claim 11, wherein the recording material is an information transmission sheet. 13. The ink jet recording method according to claim 12, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance. A colored body colored with the water-soluble azo compound according to any one of claims 1 to 7 or a salt thereof, or the ink composition according to any one of claims 8 to 10. The colored body according to claim 14, wherein the coloring is performed by an ink jet printer. An ink jet printer loaded with a container containing the ink composition according to claim 8.