TW201609988A - Water-soluble azo compound or salt thereof, ink composition, and colored body - Google Patents

Abstract

The purpose of the present invention is to provide: a water-soluble yellow colorant (compound) that is highly-soluble in water, has excellent light fastness, and has excellent coloring properties such as saturation and print density; a yellow ink composition containing the yellow colorant, said composition being used in various recording applications, particularly ink jet recording; and a colored body that has been colored by the ink composition. Specifically disclosed is an azo compound represented by the formula (1a) or a salt thereof. (In the formula: A1, A2 and T each independently represent a water-soluble substituent; each Q independently represents a hydrogen atom, a halogen atom, a sulfo group, or the like; each R independently represents a halogen atom, a C1-4 alkoxy group, or the like; y represents 0 or 1, and z represents 0 or 1, where y + z = 1; x represents an integer from 2 to 4; and a and b represent the substitution positions of A1, A2, or R.)

Description

Water-soluble azo compound or salt thereof, ink composition and color body

The present invention relates to a water-soluble azo compound or a salt thereof, an ink composition containing the azo compound or a salt thereof, and a color body obtained by coloring the same.

Among various color recording methods, a recording method by an ink jet printer is one of the representative methods, and various ink ejection methods have been developed. These ink ejection methods are used to cause ink droplets to be generated, and the ink droplets are attached to various recording materials (paper, film, cloth, etc.) for recording. Since the recording head does not directly contact the material to be recorded, it does not generate sound and is quiet. In addition, since it has features such as ease of miniaturization, high speed, and colorization, it has been rapidly popularized in recent years, and it is expected to be greatly developed in the future.

Conventionally, inks such as pens and felt-tip pens, and inks for inkjet recording have been prepared by dissolving a water-soluble dye (dye) in an aqueous medium. Among these aqueous inks, it is necessary to prevent clogging of the ink in the nib or the ink ejecting nozzle, and generally a water-soluble organic solvent is added. These inks are required to have a performance in which a recording image having a sufficient concentration can be obtained, the tip and the nozzle are not clogged, the drying property on the material to be recorded is good, the blooming is small, and the storage stability is excellent.

In the vicinity of the nozzle, the ink in the ink is clogged, and the water in the ink evaporates earlier than other solvents and additives, and the composition is in a state in which the amount of water is small and the solvent and the additive are large. In this case, the pigment is solidified and precipitated. Therefore, even in a state where the amount of moisture in the ink is small, it is difficult to precipitate solids, which is one of the most important required properties. Therefore, the high solubility of solvents and additives is also one of the properties required for pigments. Further, as a method of eliminating clogging of the nozzle, a method of using a pigment having a high printing density is known. By using a pigment having a high printing density, it is possible to reduce the pigment content in the ink while maintaining the conventional printing density. This method is not only difficult to precipitate a pigment, but also advantageous in terms of cost, and development of a dye having a high printing density is expected.

However, when an image or text information on a computer's color display is recorded in color by an inkjet printer, it is generally used by yellow (Y), magenta (M), and cyan ( Cyan) (C), black (K) 4-color ink subtractive color mixing, whereby the recorded image is expressed in color. In order to use a red (R), green (G), and blue (B) additive color mixing image in a cathode ray tube (CRT, that is, a Braun tube) display, etc., as much as possible In order to faithfully reproduce the subtractive mixed image, it is desirable that each of the pigments used in the ink, especially Y, M, and C, can each have a hue close to the standard color and be sharp. The sharpness referred to herein generally means having a high chroma. When using the three primary colors of Y, M, and C with lower chroma, the color area that can be expressed by monochromatic or mixed color becomes narrow, and the color area to be expressed The scope of the domain will become insufficient. Therefore, it is expected to develop a high chroma dye and an ink containing the pigment.

Further, the performance of the ink is required to be as follows: it is stable for long-term storage, and the density of recorded images is high, and the image is excellent in water resistance, moisture resistance, light resistance, and gas resistance.

Here, gas resistance refers to resistance to a phenomenon in which a gas (also referred to as an oxidizing gas) having an oxidation effect in air is recorded on a material to be recorded or in a material to be recorded, and an image is recorded. The pigment (dye) reacts to make the recorded image change/fade. Among the oxidizing gases, especially ozone gas, it is considered to be a main cause of promoting the change/fade phenomenon of an inkjet recorded image. This change/fade phenomenon is a peculiar phenomenon of ink-jet recorded images, and therefore, it is an important technical subject to improve ozone-resistant gas in this field.

With the development of inkjet technology in recent years, the speed of inkjet recording (printing) has been significantly improved. Therefore, like the laser printer using a toner, there is a market trend in which an inkjet printer is used for an office environment as a main use, that is, a document printing on plain paper. Inkjet printers have the advantage of not limiting the type of recording paper and the low cost of the printer itself, especially in small and medium-sized office environments such as small office/home office (SOHO). As a result, when an inkjet printer is used for printing on plain paper, the quality required for the printed matter tends to be more important in hue, color development (printing) density, and moisture resistance.

To meet these properties, a method of using a pigment ink has been proposed. However, the pigment of the pigment ink cannot be dissolved in the aqueous ink, so It is impossible to change the ink in a solution state, but an ink which exhibits a dispersed state. Therefore, if the pigment ink is used for inkjet recording, there is a problem of stability of the ink itself or a problem of clogging of the nozzle of the recording head. Moreover, when a pigment ink is used, there is often a problem in abrasion resistance. When a dye ink is used, such a problem is considered to be relatively inferior, but the dye ink is remarkably inferior to the pigment ink, particularly in terms of moisture resistance, and it is strongly desired to improve this aspect. Further, unlike the pigment ink, the dye ink adheres to the surface of the plain paper by inkjet recording, and penetrates into the back surface of the paper more quickly. As a result, the color density is liable to decrease.

As one of methods for obtaining an inkjet recorded image of a photographic quality, there is a method of providing an ink receiving layer on the surface of a material to be recorded. The ink receiving layer provided for such a purpose often contains a porous white inorganic substance in order to accelerate drying of the ink and to reduce pigmentation in a high image quality state. However, particularly in such recorded materials, the above-described change/fading due to ozone gas can be clearly observed. Recently, with the spread of digital cameras and color printers, the chances of printing images obtained by digital cameras and the like in photo quality have increased at home, and therefore, the above-mentioned images are recorded due to oxidizing gases. The change/fade is considered a problem. As for the yellow pigment, a pigment having light resistance and good resistance to oxidizing gas has been proposed as compared with magenta or cyan, which are other three primary colors. However, yellow pigments or yellow inks for inkjet recording which can sufficiently satisfy the high sharpness and various firmness required on the market have not yet appeared.

In recent years, in addition to the above-described properties, the properties possessed by the desired coloring matter are properties that are less harmful to humans and the environment. In the past, aniline derivatives used for known pigments have been proven to be highly harmful, and their use or discharge is regulated by regulations, and safety and hygiene management surfaces such as operation under extremely strict protective equipment and restrictions on the amount of residual raw materials contained in pigments are required. And in terms of productivity improvement, it has become a limiting factor.

A well-known yellow pigment for inkjet which is excellent in water solubility and vividness is C.I. (Color Index) Direct Yellow 132. Patent Documents 1 to 3 disclose an example in which C.I. (Color Index) Direct Yellow 132 is used for inkjet. Further, Patent Document 4 discloses an example in which a yellow pigment is used for inkjet, and the yellow pigment can be produced by the method disclosed in Example 1 of Patent Document 5.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 11-70729

Patent Document 2: Japanese Patent No. 3346755

Patent Document 3: Japanese Patent No. 4100880

Patent Document 4: International Publication No. 2011/122426

Patent Document 5: International Publication No. 2009/154142

An object of the present invention is to provide a water-soluble yellow pigment (compound) and various recordings containing the yellow pigment, particularly inkjet A yellow ink composition for recording, wherein the yellow pigment has high solubility in water, has high color rendering property (printing density) of a recorded image, and is excellent in chroma and light resistance.

In order to solve the above problems, the present inventors have found that a water-soluble azo compound represented by a specific formula or a salt thereof, and an ink composition containing the compound or a salt thereof can solve the above problems, and the present invention can be solved. invention.

In the formula (1), A represents a water-soluble substituent. The water-soluble substituent herein means a substituent having high hydrophilicity. That is, the present invention relates to the following.

(0)

An azo compound or a salt thereof, represented by the following formula (1);

In the formula (1), A and T each independently represent a water-soluble substituent, and each of Q and R independently represents a hydrogen atom, a halogen atom, a carboxyl group, an amine carbenyl group, a sulfo group, an amine sulfonyl group, a hydroxyl group, an amine group, and a cyanogen group. a group, a phospho group, a nitro group, a fluorenyl group, a C1 to C4 alkyl group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine formazan group, And sulfo), a C1-C4 alkoxy group (may also be substituted by one or two or more substituents, and the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group), and a C1 to C4 alkylsulfonyl group (also It may be substituted by one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, an aminomethyl group, and a sulfo group, and a C1 to C4 alkylthio group (may also be one or two or more) Substituted, and the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group, and a C1 to C4 alkylamino group (which may also be substituted by one or two or more substituents, and the substitution The group is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group, or a guanamine group, and x represents an integer of 2 to 4, and a and b represent a substitution position of A or R.

(0-1)

The azo compound or a salt thereof according to the above (0), wherein in the formula (1), the substitution position of A is a, and the substitution position of R is b.

(0-2)

The azo compound or a salt thereof according to the above (0), wherein, in the formula (1), A is a sulfo group.

(0-3)

The azo compound or a salt thereof according to the above (0), wherein, in the formula (1), x is 3, the substitution position of A is a, the substitution position of R is b, and A is a sulfo group.

(0-4)

The azo compound or a salt thereof according to the above (0), wherein, in the formula (1), x is 3, the substitution position of A is a, the substitution position of R is b, A is a sulfo group, and R is a chlorine atom. Or a methoxy group, T is a sulfo group or a carboxyl group, and Q is a chlorine atom.

(1)

An azo compound or a salt thereof, represented by the following formula (1a);

In the formula (1a), A ¹ , A ² and T each independently represent a water-soluble substituent, and Q each independently represents a hydrogen atom, a halogen atom, a carboxyl group, an amine methyl sulfonyl group, a sulfo group, an amine sulfonyl group, a hydroxyl group, an amine group. a cyano group, a phosphoric acid group, a nitro group, a decyl group or a C1 to C4 alkyl group (which may be substituted by one or two or more substituents, and the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine carbaryl group, and Sulfo), C1 to C4 alkoxy (may also be substituted by 1 or more substituents, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group), a C1 to C4 alkane a sulfo group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group), and a C1 to C4 alkylthio group (may also be one) Or substituted with two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, an aminomethyl group, and a sulfo group, and a C1 to C4 alkylamino group (which may also be substituted by one or two or more substituents) And the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group, or a guanamine group; each R independently represents a hydrogen atom, a halogen atom, an amine carbaryl group, an amine sulfonyl group, a hydroxyl group, an amine Base, cyano, nitro Mercapto group, C1~C4 alkyl group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an aminomethyl group), and a C1 to C4 alkoxy group (may also be 1) Or a substituent substituted with two or more substituents selected from a hydroxyl group and an aminomethyl sulfonyl group, and a C1 to C4 alkyl sulfo group (may be substituted by one or two or more substituents, and the substituent is Selected from a hydroxyl group and an amine methyl sulfhydryl group, a C1 to C4 alkylthio group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an amine methyl group), a C1 to C4 alkane An amine group (which may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an amine mercapto group) or a guanamine group; y represents 0 or 1, and z represents 0 or 1, but y+z=1, x represents an integer of 2 to 4, and a and b represent substitution positions of A ¹ , A ² or R.

(2)

The azo compound or a salt thereof according to the above (0) or (1), wherein, in the formula (1) or the formula (1a), x is 3.

(3)

The azo compound or a salt thereof according to the above (1) or (2), wherein, in the formula (1a), the substitution position of A ¹ is a, and the substitution position of A ² or R is b.

(4)

The azo compound or a salt thereof according to any one of the above (1), wherein, in the formula (1a), A ¹ and/or A ² is a sulfo group.

(5)

The azo compound or a salt thereof according to any one of the above (0) to (4), wherein, in the formula (1) or the formula (1a), T is a sulfo group or a carboxyl group.

(6)

The azo compound or a salt thereof according to any one of the above (0) to (5), wherein, in the formula (1) or the formula (1a), R is a chlorine atom or a methoxy group.

(7)

The azo compound or a salt thereof according to any one of the above (0) to (6), wherein, in the formula (1) or the formula (1a), Q is a chlorine atom or a bromine atom.

(8)

The azo compound or a salt thereof according to the above (1), wherein, in the formula (1a), x is 3, the substitution position of A ¹ is a, and the substitution position of A ² or R is b, A ¹ and/or A ² is a sulfo group.

(9)

The azo compound or a salt thereof according to the above (1), wherein, in the formula (1a), x is 3, the substitution position of A ¹ is a, and the substitution position of A ² or R is b, A ¹ and/or A ² is a sulfo group, R is a chlorine atom or a methoxy group, T is a sulfo group or a carboxyl group, and Q is a chlorine atom.

(10)

An ink composition containing the azo compound according to any one of the above (0) to (9) or a salt thereof.

(11)

The ink composition according to the above (10), which further contains a water-soluble organic solvent.

(12)

The ink composition according to the above (10) or (11), which is used for inkjet recording.

(13)

An ink jet recording method using the ink composition according to any one of the above (10) to (12) as an ink, and ejecting ink droplets of the ink according to a recording signal and adhering to the material to be recorded. recording.

(14)

The inkjet recording method according to (13) above, wherein the material to be recorded is a sheet for information transmission.

(15)

The inkjet recording method according to the above (14), wherein the sheet for information transfer is plain paper or a sheet having an ink receiving layer, and the ink receiving layer contains a porous white inorganic material.

(16)

A coloring body which is colored by any one of the following: (a) the azo compound according to any one of the above (0) to (9) or a salt thereof; (b) an ink composition, The ink composition contains the azo compound according to any one of the above (0) to (9) or a salt thereof; or (c) an ink composition containing the above (0) to (9) The azo compound or a salt thereof according to any one of the above, and a water-soluble organic solvent.

(17)

A coloring body obtained by coloring the inkjet recording method according to any one of (13) to (15) above.

(18)

An ink jet printer loaded with a container containing the ink composition as described in (10) or (11) above.

(19)

A method of producing the azo compound or a salt thereof according to any one of the above (0) to (0-4), which comprises the compound represented by the following formula (5) and a halogenated group The acid ester is condensed.

In the formula (5), A, T, Q, R, x, a and b have the same meanings as represented in the above formula (1);

(20)

A method of producing the azo compound or a salt thereof according to any one of the above (1) to (9), which comprises a compound represented by the following formula (5a) and a haloformate Carry out condensation;

In the formula (5a), A ¹ , A ² , T, Q, R, x, y, z, a and b have the same meanings as those represented by the above formula (1a).

The azo compound of the present invention represented by the above formula (1) or (1a) or a salt thereof has the following characteristics: it has high solubility in water, and can be said to be a water-soluble azo compound or a salt thereof, and The filterability in the process of producing the ink composition of the present invention containing the compound or a salt thereof is good, and the filterability to the membrane filter is good, for example. Further, the image recorded by the ink composition of the present invention containing the compound of the present invention is excellent in print density, chroma and light resistance as compared with an image obtained using a conventional compound. In this way, the azo compound of the present invention represented by the above formula (1) or (1a) or a salt thereof, and an ink composition containing the compound or a salt thereof are used in various ink applications for recording, in particular It is extremely useful for ink applications for inkjet recording.

The invention will be described in detail.

The azo compound of the present invention represented by the above formula (1) or a salt thereof is a water-soluble yellow pigment. In the present specification, an acidic functional group such as a sulfo group or a carboxyl group is represented by a form of a free acid unless otherwise specified. In addition, as described above, the present invention contains both the azo compound represented by the above formula (1) and the salt of the compound. However, it is often troublesome to combine the two together as a "compound or a salt thereof". Therefore, unless otherwise specified, the "(azo) compound of the present invention", that is, the "(azo) compound of the present invention," Briefly described as "the azo compound of the present invention" or "the invention" Compound." The azo compound represented by the formula (1a) or a salt thereof is also the same.

The compound of the present invention is represented by the above formula (1).

In the formula (1), x represents an integer of 2 to 4, preferably 3.

In the formula (1), A is substituted at the position of a or b, preferably at the position of a, and R is substituted at the position of a or b, preferably at the position of b. When A is substituted at the position of a, R is substituted at the position of b, and when A is substituted at the position of b, R is substituted at the position of a. Further, even when R is a hydrogen atom to be described later, it is referred to as "substitution" or the like in the present specification for the sake of convenience.

In the formula (1), A represents a water-soluble substituent. The water-soluble substituent herein means a substituent having high hydrophilicity, such as a sulfo group, a carboxyl group, a phosphoric acid group, a C1 to C4 alkyl group (substituted by one or more sulfo groups, carboxyl groups, or phosphoric acid groups), a C1 to C4 alkoxy group (substituted by one or more sulfo groups, a carboxyl group, or a phosphate group) or a C1 to C4 alkylsulfonyl group (substituted by one or more sulfo groups, carboxyl groups, or phosphoric acid groups), C1 to C4 alkylthio group (substituted by one or more sulfo groups, carboxyl groups, or phosphoric acid groups), C1 to C4 alkylamino group (substituted by one or more sulfo groups, carboxyl groups, or phosphoric acid groups), etc. . Among them, a sulfo group or a carboxyl group is further preferred, and a sulfo group is more preferred.

In the formula (1), T represents a water-soluble substituent. The water-soluble substituent herein means a substituent having high hydrophilicity, such as a sulfo group, a carboxyl group, a phosphoric acid group, a C1 to C4 alkyl group (substituted by one or more sulfo groups, carboxyl groups, or phosphoric acid groups), a C1 to C4 alkoxy group (substituted by one or more sulfo groups, a carboxyl group, or a phosphate group) or a C1 to C4 alkylsulfonyl group (by one or more sulfo groups, a carboxyl group or a phosphate group substituted, a C1 to C4 alkylthio group (substituted by one or more sulfo groups, a carboxyl group, or a phosphoric acid group) or a C1 to C4 alkylamino group (one or more sulfo groups, A carboxyl group or a phosphate group is substituted). Among them, a sulfo group or a carboxyl group is further preferred.

A and T may be the same, may be different, and are preferably the same.

Q and R each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an amine mercapto group, a sulfo group, an amine sulfonyl group, a hydroxyl group, an amine group, a cyano group, a phosphate group, a nitro group, a decyl group, or a C1 to C4 alkyl group ( It may be substituted by one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, an aminomethyl group, and a sulfo group, and a C1 to C4 alkoxy group (may also be one or two). The above substituent is substituted, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group, and a C1 to C4 alkylsulfonyl group (may be substituted by one or two or more substituents, and The substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group, and a C1 to C4 alkylthio group (which may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and a carboxyl group. , aminyl, and sulfo), C1 to C4 alkylamino (which may also be substituted by one or two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfonate) The base or the amidino group, Q is preferably a halogen atom, and more preferably a chlorine atom. R is preferably a halogen atom, a hydroxyl group, an amine group, or a C1 to C4 alkoxy group (may be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo), a C1 to C4 alkylthio group (which may be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group), and more preferably a halogen atom, a C1 to C4 alkoxy group (may also be substituted by one or two or more substituents, and the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, and an amine group The mercapto group and the sulfo group are more preferably a halogen atom or a C1 to C4 alkoxy group substituted with no substituent, and more preferably a chlorine atom or a methoxy group. The mercapto group is preferably a C1 to C4 alkano group, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. As the guanamine group, an amine group substituted with one of the above thiol groups is preferred.

Among the above-mentioned substitution positions of x, Q, A, T and R, more preferred are compounds which are preferably combined, and more preferably a compound which is further preferably combined. The same applies to the combination of the preferred one and the preferred one.

The azo compound represented by the above formula (1) or a salt thereof is preferably an azo compound represented by the above formula (1a) or a salt thereof. A of the formula (1) can be represented by the formula (1a) as A ¹ and (A ² ) _y (y represents 0 or 1). R of the formula (1) can be represented by the formula (1a) as (R) _z (z represents 0 or 1). y+z=1. y is preferably 0, and z is preferably 1.

In the formula (1a), A ¹ and A ² each independently represent a water-soluble substituent. The water-soluble substituent has the same meaning as the water-soluble substituent of the formula (1).

In the formula (1a), R each independently represents a hydrogen atom, a halogen atom, an amine carbenyl group, an amine sulfonyl group, a hydroxyl group, an amine group, a cyano group, a nitro group, a fluorenyl group, a C1 to C4 alkyl group (may also be 1). Substituted with two or more substituents, and the substituent is selected from a hydroxyl group and an amine mercapto group), a C1 to C4 alkoxy group (may also be substituted by one or two or more substituents, and the substitution The group is selected from the group consisting of a hydroxyl group and an amine carbenyl group, and a C1 to C4 alkylsulfonyl group (which may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an amine mercapto group), a C1~C4 alkylthio group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an amine mercapto group), and a C1 to C4 alkylamino group (may also be one or Two or more substituents are substituted, and the substituent is selected from a hydroxyl group and an amine mercapto group, or a guanamine group. In the formula (1a), preferred R, further preferably R, more preferably R and further preferably R are the same as those of R of the formula (1).

In the formula (1a), a and b represent the substitution positions of A ¹ , A ² or R. When A ¹ is substituted at the position of a, A ² or R is substituted at the position of b, and when A ¹ is substituted at the position of b, A ² or R is substituted at the position of a. Preferably, A ¹ is substituted at the position of a, and A ² or R is substituted at the position of b. Further, it is preferred that A ¹ is substituted at the position of a, and A ² or R is substituted at the position of b. In the latter case, z is 1, and y is 0.

In the formula (1a), T, Q and x are the same as T, Q and x in the formula (1).

The compound of the present invention represented by the above formula (1) can be produced, for example, in the following manner. Further, x, A, T, R, Q, a, and b which are suitably used in the following formulas (2a), (3a), (4), and (5) respectively represent the same as in the above formula (1). significance.

The compound represented by the following formula (2a) is converted into a methyl-ω-sulfonic acid derivative represented by the following formula (3a) using sodium hydrogen sulfite and an aqueous formaldehyde solution.

Preferably, the compound represented by the following formula (2) is converted into a methyl-ω-sulfonic acid derivative represented by the following formula (3) using sodium hydrogen sulfite and an aqueous formaldehyde solution.

Next, the compound represented by the following formula (4) is subjected to diazotization by a general method, and the methyl-ω-sulfonic acid derivative represented by the formula (3a) obtained previously is at a reaction temperature of 0~. The coupling reaction is carried out under the conditions of a pH of 4 to 6 at 15 ° C, and then a hydrolysis reaction is carried out under the conditions of a reaction temperature of 80 to 95 ° C and a pH of 10.5 to 11.5, whereby a compound represented by the following formula (5) can be obtained. Further, the present synthesis is a method based on the method described in International Publication No. 2011/122426.

Next, the compound (2 mol) represented by the above formula (5) and a haloformate (1 mol), for example, p-nitrophenyl chloroformate (1 mol) at a reaction temperature of 30 to 60 ° C and a pH of 4 to 8 are used. Condensation is carried out under the conditions, whereby the compound of the present invention represented by the above formula (1) can be obtained.

The compound represented by the above formula (4) and the compound represented by the above formula (5) are preferably each a compound represented by the formula (4a) and the formula (5a). In this case, the above formula (1a) can be obtained. ) the azo compound represented.

Specific examples of the compound of the present invention represented by the above formula (1) are shown in Tables 1 to 7 below. However, the invention is not limited to the specific examples. In Tables 1 to 7, the sulfo group or the carboxyl group is represented by the form of the free acid. Tables 1 to 7 also show specific examples of the compound of the present invention represented by the formula (1a). In this case, when y of the formula (1a) is 0, A of Tables 1 to 7 corresponds to the formula ( 1a) A ¹ .

The compound of the above formula (1) (comprising the compound of the formula (1a), hereinafter the same) may also exist in the form of a free acid or a salt thereof. The salt of the compound represented by the above formula (1) includes a salt formed with an inorganic or organic cation. Specific examples of the salt of the inorganic cation include an alkali metal salt such as a salt such as a lithium salt, a sodium salt or a potassium salt; and an ammonium salt (NH ₄ ⁺ ). In addition, as a specific example of the salt of the organic cation, for example, the quaternary ammonium salt represented by the following formula (6) is mentioned, but it is not limited to this.

In the above formula (6), Z ¹ to Z ⁴ each independently represent a hydrogen atom, a C1 to C4 alkyl group, a hydroxyl group C1 to C4 alkyl group, or a hydroxyl group C1 to C4 alkoxy group C1 to C4 alkyl group, and Z ¹ to Z At least one of ⁴ is a group other than a hydrogen atom.

Here, examples of the C1 to C4 alkyl groups in Z ¹ to Z ⁴ include a methyl group and an ethyl group. Similarly, examples of the above-mentioned hydroxy C1 to C4 alkyl group include a methylol group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and 2 - Hydroxybutyl and the like. Similarly, examples of the hydroxy C1 to C4 alkoxy C1 to C4 alkyl group include a hydroxyethoxymethyl group, a 2-hydroxyethoxyethyl group, and a 3-(hydroxyethoxy)propyl group. 3-(hydroxyethoxy)butyl, 2-(hydroxyethoxy)butyl and the like.

Among the above salts, preferred are alkali metal salts such as sodium, potassium and lithium; monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and the like. An organic quaternary ammonium salt such as a salt of diisopropanolamine or triisopropanolamine; an ammonium salt; Among them, lithium salts, sodium salts, and ammonium salts are further preferred.

As is well known to those skilled in the art, the salt or free acid of the compound of the above formula (1) can be easily obtained by the following method or the like.

For example, in the synthesis reaction of the compound of the formula (1), the reaction liquid after completion of the final step or an aqueous solution containing a salt of the compound of the formula (1) or the like is precipitated by the following method to precipitate a solid. By filtration and separation, a sodium salt or the like of the compound of the above formula (1) in a wet cake form can be obtained, and the method is, for example, a method of adding a water-soluble organic solvent such as acetone or a C1-C4 alcohol; A method of salting out sodium chloride.

In addition, after the wet cake of the obtained sodium salt is dissolved in water, an acid such as hydrochloric acid is added thereto to appropriately adjust the pH value, and the precipitated solid is subjected to filtration separation, whereby the compound of the above formula (1) can be obtained. A free acid, or a compound of formula (1) which is partially a sodium salt, that is, a mixture of the free acid and the sodium salt of the compound of formula (1).

Further, after the obtained wet cake of the sodium salt or the dried solid thereof is dissolved in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added thereto to appropriately adjust the pH, for example, to pH 1 to 3, and The precipitated solid is subjected to filtration separation, whereby an ammonium salt of the compound of the above formula (1) can be obtained. By appropriately adjusting the amount of ammonium chloride added or/and the pH value, a mixture of the ammonium salt of the compound of the formula (1) and the sodium salt of the compound of the formula (1); or the free acid of the compound of the formula (1) can be obtained. Mixture with ammonium salts, etc.

Further, as described later, a mineral acid (for example, hydrochloric acid or sulfuric acid) may be added to the reaction liquid after completion of the above reaction to directly obtain a solid of a free acid. In this case, the wet cake of the free acid of the compound of the formula (1) is added to water and stirred, and then, for example, potassium hydroxide, lithium hydroxide, aqueous ammonia, or an organic quaternary ammonium hydroxide of the formula (6) is added. By salting, a potassium salt, a lithium salt, an ammonium salt, or a quaternary ammonium salt corresponding to the compound to be added individually can be obtained. By limiting the number of moles of the hydroxide or the like added to the molar amount of the free acid, for example, a mixed salt of a lithium salt and a sodium salt can be prepared, and a lithium salt or a sodium salt can be prepared. And a mixed salt of an ammonium salt. The salt of the compound of the above formula (1) may have physical properties such as solubility or the performance of the ink when used as an ink, and may vary depending on the type of the salt. Therefore, it is preferable to select the kind of salt in accordance with the intended ink performance and the like.

The compound of the present invention of the above formula (1) is capable of separating a solid free acid by adding a mineral acid such as hydrochloric acid after completion of the reaction, and by using the solid of the free acid obtained as water or water such as hydrochloric acid. The acidic salt (inorganic impurities) contained in the impurities, such as sodium chloride or sodium sulfate, can be removed by washing with acidic water or the like. The free acid of the compound of the present invention obtained as described above can be obtained by treating the obtained wet cake or its dried solid in water with a desired inorganic base or organic base as described above to obtain a corresponding compound. a solution of salt. Examples of the inorganic base include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate; and ammonium hydroxide (ammonia). ;Wait. As an organic base, for example, it corresponds to the above The quaternary ammonium organic ammonium represented by the formula (6), such as an alkanolamine such as diethanolamine or triethanolamine, is not limited thereto.

The compound of the present invention is suitable for dyeing natural or synthetic fiber materials or blended products, and is also suitable for use in writing inks and ink composition for inkjet recording. For example, in the synthesis reaction of the compound of the present invention of the above formula (1), the reaction liquid after the final step can be directly used in the production of the ink composition of the present invention. However, for example, the reaction solution or the like may be dried by the above method or spray drying to separate the compound, and then the obtained compound may be processed into an ink composition.

The ink composition of the present invention is a mixed solution (also referred to as an aqueous medium) in which the compound of the above formula (1) is dissolved in water or dissolved in water and a water-soluble organic solvent (an organic solvent which can be mixed with water). Add an ink preparation as needed. When the ink composition is used as an ink for an ink jet printer, it is preferable to use a substance having a small content of inorganic impurities contained as an impurity, wherein the inorganic impurity means a chloride of a metal cation, for example, Sodium chloride; a sulfate of a metal cation such as sodium sulfate or the like. In this case, for example, the total content of sodium chloride and sodium sulfate is about 1% by mass or less with respect to the total mass of the compound of the formula (1), and the lower limit is 0% by mass, that is, detection by a detecting instrument. Below the limit. Examples of the method for producing a compound having less inorganic impurities include the following methods: a method of reverse osmosis membrane known per se; or a dry product or a wet cake of the compound of the present invention such as acetone or C1~ In a water-soluble organic solvent such as C4 alcohol (such as methanol, ethanol, isopropanol, etc.), or added to a water-soluble organic solvent In the solvent, a method of performing suspension purification or crystallization, or the like, and a desalting treatment or the like may be carried out by such methods.

The ink composition of the present invention usually contains the compound of the above formula (1) in an amount of 0.1 to 20% by mass, preferably 1 to 10% by mass, and more preferably 2 to 8% by mass based on the total mass of the ink composition. %.

The ink composition of the present invention may be prepared by using water as a medium, or may contain a water-soluble organic solvent or an ink preparation agent as needed within a range that does not impair the effects of the present invention.

The purpose of using a water-soluble organic solvent is to achieve the following effects: dissolving the dye, preventing the drying of the composition (maintaining a wet state), adjusting the viscosity of the composition, promoting the penetration of the dye into the recorded material, and adjusting the surface tension of the composition. , defoaming of the composition, and the like. The ink composition of the present invention preferably contains a water-soluble organic solvent.

Examples of the ink preparation agent include an antiseptic and antifungal agent, a pH adjuster, a chelating agent, a rust preventive, an ultraviolet absorber, a viscosity adjuster, a dye dissolving agent, a fading preventing agent, a surface tension adjusting agent, and an antifoaming agent. And other known additives.

The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, based on the total mass of the ink composition of the present invention, and the ink preparation agent is used in an amount of 0 to 20% by mass, preferably 0. ~15% by mass. In addition to the compound of the above formula (1), the water-soluble organic solvent, and the ink preparation agent, the ink composition of the present invention is water.

Examples of the water-soluble organic solvent include C1 to C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol; , N-dimethylformamide, N,N-dimethylacetamide and other guanamines; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidine Heterocyclic ketones such as ketone, 1,3-dimethylimidazolidin-2-one, or 1,3-dimethylhexahydropyrimidin-2-one; acetone, methyl ethyl ketone, 2-methyl-2 a ketone or keto alcohol such as hydroxypentan-4-one; a cyclic ether such as tetrahydrofuran or dioxane; ethylene glycol, 1,2-propanediol or 1,3-propanediol, 1,2-butyl Glycol or 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, sulfur diethylene glycol Mono-, oligo, polyalkylene glycol, or thioethylene glycol having a C2~C6 alkylene unit; a polyol such as trimethylolpropane, glycerin, hexane-1,2,6-triol (more Good is triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), C1 ~ C4 monoalkyl ether, ethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other polyhydric alcohols; [gamma] -butyrolactone; dimethyl sulfoxide; and the like.

Further, the above-mentioned water-soluble organic solvent also contains a substance which is solid at normal temperature, such as trimethylolpropane. However, these substances exhibit water solubility even in the case of solids, and further, aqueous solutions containing such substances exhibit the same properties as water-soluble organic solvents, and it is expected that these substances have the same effects as water-soluble organic solvents. To use. Therefore, in this specification, for the sake of convenience, even this solid substance is only It is used for the same purpose as above, that is, it is included in the range of a water-soluble organic solvent.

As the above water-soluble organic solvent, preferred are isopropyl alcohol, glycerin, monoethylene glycol, diethylene glycol, or triethylene glycol, dipropylene glycol, 2-pyrrolidone, hydroxyethyl-2-pyrrolidine. Ketone, 1,3-dimethylimidazolidin-2-one, N-methyl-2-pyrrolidone, trimethylolpropane, and butyl carbitol, and further preferably isopropanol, glycerol , diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, butyl carbitol. These water-soluble organic solvents may be used singly or in combination.

Examples of the antiseptic and antifungal agent include an organic sulfur system, an organic nitrogen sulfur system, an organic halogen system, a haloallyl oxime system, an iodopropargyl group, an N-haloalkylthio group, and a benzothiazole. , nitrile, pyridine, 8-hydroxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium, triazine A compound such as a thiadiazine system, a guanamine benzene system, an adamantane system, a dithiocarbamate system, a bromofluorenone system, a benzyl bromoacetate system or an inorganic salt system.

The organic halogen compound may, for example, be sodium pentachlorophenolate.

The oxidized pyridine compound may, for example, be sodium 2-pyridinethiol-1-oxide.

Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl. -4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3- Ketone magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, and the like.

Examples of the other antiseptic and antifungal agents include sodium acetate, sodium sorbate, and sodium benzoate; and further, trade names PROXEL ^RTM GXL (S) and PROXEL ^RTM XL-2 (S) manufactured by Arch Chemicals, Inc. )Wait. In addition, in this specification, the superscript "RTM" means a registered trademark.

The pH adjuster is used for the purpose of improving the storage stability of the ink, and any substance can be used as long as the pH of the ink can be controlled in the range of 6.0 to 11.0. Examples thereof include alkanolamines such as diethanolamine and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide; or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. Carbonate; aminesulfonic acid such as taurine.

Examples of the chelating agent include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenediaminepentaacetate, and sodium uracildiacetate.

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

Examples of the ultraviolet absorber include a benzophenone compound, a benzotriazole compound, a cinnamic acid compound, a triazine compound, and a stilbene compound. Further, a compound represented by a benzoxazole-based compound which absorbs ultraviolet rays and emits fluorescence, that is, a fluorescent whitening agent or the like can be used.

Examples of the viscosity adjuster include, in addition to the water-soluble organic solvent, a water-soluble polymer compound such as polyvinyl alcohol, a cellulose derivative, a polyamine, a polyimine or the like.

Examples of the dye dissolving agent include urea, ε-caprolactam, and ethyl carbonate. Among them, urea is preferably used.

The fading preventing agent is used for the purpose of improving the preservation of an image. As the fading preventing agent, various organic and metal complex-based fading preventing agents can be used. Examples of the organic fading preventing agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, decanes, and dihydrobenzopyran ( The chromane), the alkoxyaniline, and the heterocyclic ring; and the metal complex may, for example, be a nickel complex or a zinc complex.

The surface tension adjusting agent may, for example, be an anionic surfactant, an amphoteric surfactant, a cationic surfactant, a nonionic surfactant or the like.

Examples of the anionic surfactant include an alkylsulfonyl carboxylate, an α-olefinsulfonate, a polyoxyethylene alkyl ether acetate, an N-decylamino acid and a salt thereof, and an N-methylmethyl group. Taurine, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl sulfate, alkylphenol type Phosphate ester, alkyl type phosphate, alkyl aryl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate, and the like.

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

Examples of the amphoteric surfactant include: lauryl dimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium salt betaine, and coconut oil fatty acid amidoxime. Dimethylaminoacetic acid betaine, polyoctyl polyaminoethylglycine, other imidazoline derivatives, and the like.

Examples of the nonionic surfactant include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, and polyoxyethylene lauryl ether. An ether system such as polyoxyethylene alkyl ether; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate , sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate and other ester systems; 2,4,7,9-tetramethyl-5-decyne-4,7- Ethylene glycol (alcohol) such as diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol; Trade names manufactured by the company, SURFYNOL ^RTM 104, SURFYNOL ^RTM 82, SURFYNOL ^RTM 465, OLFINE ^RTM STG; Sigma-Aldrich, Inc., trade name Tergitol ^RTM 15-S-7.

Examples of the antifoaming agent include a highly oxidized oil system, a glycerin fatty acid ester system, a fluorine system, and a ruthenium compound.

These ink preparation agents can be used singly or in combination. Further, the surface tension of the ink composition of the present invention is generally 25 to 70 mN/m, preferably 25 to 60 mN/m, and the viscosity is preferably 30 mPa. s below, and further preferably adjusted to 20mPa. s below.

In the production of the ink composition of the present invention, the order in which various chemical agents such as additives are dissolved is not particularly limited. The water for modulating the ink composition is preferably one having less impurities such as ion-exchanged water or distilled water. Further, after the ink composition is prepared as needed, microfiltration may be performed using a membrane filter or the like to remove the impurities in the ink composition. In particular, when the ink composition of the present invention is used as an ink for inkjet recording, it is preferred to carry out microfiltration. The pore size of the filter used for microfiltration is generally from 1 μm to 0.1 μm, preferably from 0.8 μm to 0.1 μm.

The ink composition containing the compound of the present invention is suitably used for printing, photocopying, marking, writing, drawing, printing, or recording (printing), and is particularly suitable for use in inkjet recording. Further, the ink composition of the present invention does not easily precipitate solids even when it is dry in the vicinity of the nozzle of the recording head of the ink jet printer, and therefore, it is less likely to cause clogging of the recording head.

As a method of recording on a recording material by the inkjet recording method of the present invention, the following method can be mentioned. That is, the container filled with the ink composition of the present invention is loaded into a specific position of the ink jet printer, and the ink composition of the present invention is used as an ink, and the ink droplets of the ink are ejected in accordance with the recording signal. A method of recording materials for recording. Among the ink jet printers, there are ink jet printers using the following methods, for example, a piezo method using mechanical vibration, and a bubble jet (registered trademark) method using air bubbles generated by heating. Wait. The ink jet recording method of the present invention can be used in any manner.

For the purpose of obtaining finer recorded images, two types of inks containing the same pigment are sometimes loaded into an inkjet printer. The two kinds The difference in ink is the content of the dye, and the content of one of the pigments is high, and the content of the other is low, and the two inks are used as an ink set. The ink composition of the present invention can also be used as such an ink set. Further, the ink composition of the present invention can be used for one of the ink groups, and a known ink (composition) can be used for the other.

The ink composition of the present invention can also form a yellow ink composition containing the compound of the present invention and a known yellow color within the range of not obstructing the effects obtained by the present invention. pigment. Further, the ink of the other color may be used in combination with the magenta dye or the cyan pigment, for example, in the coloring application of the black ink or in the case of blending the red ink or the green ink. Further, in order to obtain a full-color recorded image, the ink composition of the present invention may also be various colors such as magenta, cyan, and desired green, blue (or purple), red, and black. The ink is combined for use. At this time, inks of various colors are filled into respective containers, and these containers are loaded into a specific position of the ink jet printer, and then used for inkjet recording.

Examples of the recording material to be used in the ink jet recording method of the present invention include sheets for information transmission such as paper and film, fibers or cloth (cellulose, nylon, wool, etc.), leather, and color filters. A substrate or the like; preferably a sheet for information transfer. The sheet for information transfer is not particularly limited, and it is possible to use plain paper, and it is also possible to use a surface-treated object, specifically, an ink receiving layer on a substrate such as paper, synthetic paper, or film. Things and so on. The ink receiving layer refers to a layer having an action of absorbing ink and accelerating drying of the ink. The ink receiving layer is set by the following method: For example, a method of impregnating or coating a cationic polymer on the substrate; and inorganic fine particles capable of absorbing a pigment in the ink are applied to the surface of the substrate together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone Method etc. Examples of the material of the inorganic fine particles capable of absorbing the dye in the ink include porous cerium oxide, alumina sol, and special ceramics.

Such a sheet for information transfer having an ink receiving layer is generally referred to as an ink jet paper, an ink jet film, a glossy paper, a glossy film, or the like. As an example of a typical commercial product of the sheet for information transmission having an ink receiving layer, Canon Co., Ltd., trade name Professional Photo paper, Canon Photo Paper Glossy Pro (Platinum Grade), and Glossy Gold; Seiko Epson Co., Ltd., product name: Photo Paper CRISPIA (High Gloss), Photo Paper (Glossy); manufactured by Hewlett-Packard Japan Co., Ltd., trade name Advanced Photo Paper (Glossy); manufactured by Fujifilm Co., Ltd., trade name: KASSAI SHASHIN -SHIAGE Pro; manufactured by Brother Industries, Inc., trade name: Photo Glossy Paper BP71G, etc.

Further, plain paper means, in particular, paper which is not provided with an ink receiving layer, and various types of products are widely sold in the market depending on the use thereof. Among the commercially available plain papers, two-side high-quality plain paper (made by Seiko Epson Co., Ltd.); PB PAPER GF-500 (made by Canon Co., Ltd.); Multipurpose Paper, All-in -one Printing Paper (manufactured by Hewlett-Packard Co., Ltd.) and the like. Further, in particular, paper for plain paper copy (PPC), which is not limited to inkjet recording, is also plain paper.

The color body of the present invention refers to a substance colored by any of the following three: (a) a water-soluble azo compound of the present invention or a salt thereof; (b) an ink composition of the present invention, It contains the compound or a salt thereof; (c) an ink composition of the present invention, which contains the compound or a salt thereof, and a water-soluble organic solvent. The material to be colored is not particularly limited, and examples thereof include the above-described recording materials, but are not limited thereto. Preferably, the above-mentioned recorded material is colored. The method of coloring the substance is not particularly limited, and examples thereof include a printing method such as a dip dyeing method, a printing method, and a screen printing method, and an ink jet recording method of the present invention. The ink jet recording method of the present invention is preferred. Among the above colored bodies, a color body which is colored by the ink jet recording method of the present invention is preferred.

The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof is excellent in solubility in water or a water-soluble organic solvent. Further, this compound is characterized in that the filterability in the process of producing the ink composition of the present invention is excellent, for example, the filterability of the membrane filter. The ink composition of the present invention can obtain a yellow recorded image on a recording material such as plain paper and a sheet for information transfer having an ink receiving layer, which is very vivid, has a high chroma and a high print density. For the ideal hue. Therefore, a photo-style color image can be faithfully reproduced on paper. Further, after the ink composition of the present invention is stored for a long period of time, there is no solid precipitation, physical property change, or hue change, and the storage stability is extremely excellent.

Even when the ink composition of the present invention is used as the inkjet ink, the solid deposition of the ink composition in the vicinity of the nozzle is not easily generated, and the ejector (recording head) is not clogged. Further, the ink composition of the present invention, whether using a continuous ink jet printer to recirculate ink at a long time interval, or by on-demand inkjet printing In the case of intermittent use, no physical changes will occur.

Further, the ink composition of the present invention has various properties such as water resistance, moisture resistance, ozone gas resistance, abrasion resistance, and light resistance, which are recorded on the information transfer sheet having the ink receiving layer. It is excellent in properties, especially in light resistance, and therefore, the photo-style image is excellent in long-term storage stability. Further, compared with the conventional ink, color rendering properties such as saturation, brightness, and printing density on glossy paper are excellent, and in particular, it is excellent in chroma.

In this way, the water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof, and the ink composition of the present invention containing the water-soluble azo compound or a salt thereof are used in various recording ink applications. It is extremely useful for ink applications for inkjet recording.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. In addition, unless otherwise stated, "parts" and "%" in this document refer to the mass basis, and the reaction temperature is the internal temperature. Among the synthesized compounds, the measurement of λ max (maximum absorption wavelength) is a measured value expressed in an aqueous solution of pH 7-8. Also, implementation In each structural formula of the compound obtained in the example, an acidic functional group such as a carboxyl group or a sulfo group is described in the form of a free acid.

[Material Synthesis]

To 100 parts of N,N-dimethylformamide, 22.5 parts of 2-acetamido-4-chlorophenol and 16.8 parts of potassium carbonate were added, and the mixture was heated to 80-90 ° C and stirred for 1 hour. 20.3 parts of ethyl bromobutyrate diluted with 50 parts of N,N-dimethylformamide was added dropwise thereto for about 30 minutes. After the reaction was carried out for 1 hour at the same temperature, the mixture was cooled to room temperature and 200 parts of water was added thereto, and the mixture was stirred for 1 hour, and the precipitated solid was separated by filtration, and the obtained wet cake was dispersed in 400 parts of water to oxidize. After the sodium was adjusted to pH 11, the mixture was stirred at 80 to 95 ° C for 5 hours while maintaining the same pH value. Further, 80 parts of sodium chloride was added to the obtained solution of the reaction liquid, and the mixture was stirred for 1 hour to precipitate. The solid was separated by filtration, whereby a wet cake containing 5-chloro-2-(3-carboxypropoxy)aniline was obtained. The obtained wet cake was washed with 200 parts of isopropyl alcohol, and the obtained wet cake was dried by a hot air dryer at 80 ° C, thereby obtaining 5-chloro-2-(3-carboxypropoxy). Aniline 27.0 parts.

[(A) Synthesis of Dyes] [Example 1] (step 1)

24.9 parts of 5-amino-2-chlorobenzenesulfonic acid was dissolved in 200 parts of water while adjusting to pH 6 with sodium hydroxide, and then 8.7 parts of sodium nitrite was added. The solution is taken at 0 to 10 ° C for 30 minutes. After 200 parts of 5% hydrochloric acid, the mixture was stirred at 10 ° C or lower for 1 hour to carry out a diazotization reaction to prepare a diazo reaction solution.

On the other hand, 26.2 parts of 5-chloro-2-(3-sulfopropoxy)aniline was dissolved in 130 parts of water while adjusting to pH 7 with sodium hydroxide, and 11.4 parts of sodium hydrogen sulfite and 9.4 parts of a 35% aqueous formaldehyde solution was prepared as a methyl-ω-sulfonic acid derivative by a general method.

The obtained methyl-ω-sulfonic acid derivative was added to the previously prepared diazo reaction solution, and stirred at 0 to 15 ° C and pH 4 to 7 for 24 hours. After the reaction liquid was adjusted to pH 11 with sodium hydroxide, the mixture was stirred at 80 to 95 ° C for 5 hours while maintaining the same pH value, and further 200 parts of sodium chloride was added to the obtained solution of the reaction liquid. After stirring for 1 hour, the precipitated solid was separated by filtration, whereby 80 parts of the azo compound represented by the following formula (7) in a wet cake state was obtained.

(Step 2)

65 parts of the wet cake of the compound represented by the above formula (7) was dissolved in 200 parts of warm water at 60 ° C, and 5 parts of p-nitrophenyl chloroformate was added over 2 hours. During the input process, the solution was adjusted to pH 5.0 to 7.0 by sodium carbonate, and the liquid temperature was adjusted to 55 to 65 °C. After completion of the reaction, 40 parts of sodium chloride was added to the solution, and the mixture was stirred for 1 hour, and the precipitated solid was separated by filtration, whereby 35 parts of a wet cake was obtained. The wet cake was added to 100 parts of water, stirred and dissolved, and then adjusted to pH 8-9 by adding a 25% aqueous sodium hydroxide solution. 400 parts of 2-propanol was added to the aqueous solution, and the precipitated solid was separated by filtration to obtain a wet cake, and the wet cake was dried by a hot air dryer at 80 ° C to obtain the following formula (8). The sodium salt (λ _max : 421.0 nm) of the water-soluble azo compound of the present invention is represented by 13.3 parts.

[Embodiment 2] (step 1)

In the above Example 1 (Step 1), 24.4 parts of 3-amino-4-methoxybenzenesulfonic acid was used instead of 24.9 parts of 5-amino-2-chlorobenzenesulfonic acid, and 5-chloro-2 was used. The azo compound 80 represented by the following formula (9) in the form of a wet cake was obtained in the same manner as in the step 1 of the first embodiment except that the amount of the (3-sulfopropoxy)aniline was 26.2 parts. Share.

(Step 2)

65 parts of the wet cake of the compound represented by the above formula (9) was dissolved in 200 parts of warm water at 60 ° C, and 5 parts of p-nitrophenyl chloroformate was added over 2 hours. During the input process, the solution was adjusted to pH 5.0 to 7.0 by sodium carbonate, and the liquid temperature was adjusted to 55 to 65 °C. After completion of the reaction, 40 parts of sodium chloride was added to the solution, and the mixture was stirred for 1 hour, and the precipitated solid was separated by filtration, whereby 35 parts of a wet cake was obtained. The wet cake was added to 100 parts of water, stirred and dissolved, and then adjusted to pH 8-9 by adding a 25% aqueous sodium hydroxide solution. 400 parts of 2-propanol was added to the aqueous solution, and the precipitated solid was separated by filtration to obtain a wet cake, and the wet cake was dried by a hot air dryer at 80 ° C to obtain the following formula (10). The sodium salt (λ _max : 416.0 nm) of the water-soluble azo compound of the present invention represented by 13.3 parts.

[Example 3] (step 1)

In the above Example 1 (Step 1), except that 31.1 parts of 5-bromo-2-(3-sulfopropoxy)aniline was used instead of 26.2 parts of 5-chloro-2-(3-sulfopropoxy)aniline, The rest are in the same manner as step 1 of the embodiment 1. 80 parts of the azo compound represented by the following formula (12) in a wet cake state was obtained.

(Step 2)

70 parts of the wet cake of the compound represented by the above formula (12) was dissolved in 200 parts of warm water at 60 ° C, and 5 parts of p-nitrophenyl chloroformate was added over 2 hours. During the input process, the solution was adjusted to pH 5.0 to 7.0 by sodium carbonate, and the liquid temperature was adjusted to 55 to 65 °C. After completion of the reaction, 40 parts of sodium chloride was added to the solution, and the mixture was stirred for 1 hour, and the precipitated solid was separated by filtration, whereby 35 parts of a wet cake was obtained. The wet cake was added to 100 parts of water, stirred and dissolved, and then adjusted to pH 8-9 by adding a 25% aqueous sodium hydroxide solution. 400 parts of 2-propanol was added to the aqueous solution, and the precipitated solid was separated by filtration to obtain a wet cake, and the wet cake was dried by a hot air dryer at 80 ° C to obtain the following formula (13). The sodium salt (λ _max : 418.0 nm) of the water-soluble azo compound of the present invention represented by 14.4 parts.

[Example 4] (step 1)

In the above Example 1 (Step 1), except that 23.0 parts of 5-chloro-2-(3-carboxypropoxy)aniline was used instead of 26.2 parts of 5-chloro-2-(3-sulfopropoxy)aniline, The rest were carried out in the same manner as in the step 1 of Example 1, and 80 parts of the azo compound represented by the following formula (14) in a wet cake state was obtained.

(Step 2)

61 parts of the wet cake of the compound represented by the above formula (14) was dissolved in 200 parts of warm water at 60 ° C, and 5 parts of p-nitrophenyl chloroformate was added over 2 hours. During the input process, the solution was adjusted to pH 5.0 to 7.0 by sodium carbonate, and the liquid temperature was adjusted to 55 to 65 °C. After completion of the reaction, 40 parts of sodium chloride was added to the solution, and the mixture was stirred for 1 hour, and the precipitated solid was separated by filtration, whereby 35 parts of a wet cake was obtained. The wet cake was added to 100 parts of water, stirred and dissolved, and then adjusted to pH 8-9 by adding a 25% aqueous sodium hydroxide solution. 400 parts of 2-propanol was added to the aqueous solution, and the precipitated solid was separated by filtration to obtain a wet cake, and the wet cake was dried by a hot air dryer at 80 ° C to obtain the following formula (15). The sodium salt (λ _max : 417.0 nm) of the water-soluble azo compound of the present invention represented by 12.4 parts.

[(B) Modulation of ink] [Example 5]

The azo compound of the present invention obtained in the above Example 1 "the sodium salt of the compound represented by the formula (8)" was used as a dye, and the components shown in the following Table 8 were mixed to prepare a solution, thereby obtaining the present. Inventive ink composition. The obtained ink compositions were each filtered through a 0.45 μm membrane filter to remove the impurities, and the ink for the test was prepared. Further, the pH of the test ink was in the range of 8.0 to 9.5. In the following Table 8, the "surfactant" is a product name Surfynol ^RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. An ink prepared by using the compound obtained in Example 1 was used as Example 5. Further, the composition shown in the following Table 8 was mixed and carried out in the same manner, and then an ink prepared by using the compound obtained in Example 2 was used as Example 6.

Further, the components shown in the following Table 9 were mixed and carried out in the same manner, and then the ink prepared by using the compound obtained in Example 3 was used as Example 7, and the use was carried out by using The ink prepared by the compound obtained in Example 4 was designated as Example 8. In Table 9, the "surfactant" is also a trade name of Surfynol ^RTM 104PG50 manufactured by Nissin Chemical Co., Ltd.

[Comparative Examples 1, 2]

The compound (5) (compound represented by the following formula (11)) described in the above Patent Document 4 is used in place of the compound of the present invention obtained by the example 1, and the rest is the same as in the example 5. The way to modulate the ink used for comparison. The preparation of this ink was made into Comparative Example 1.

In addition, the compound (5) (the compound represented by the following formula (11)) described in the above Patent Document 4 is used instead of the compound of the present invention obtained by the example 1, and the examples are the same as the examples. 7 The same method is used to modulate the ink for comparison. The preparation of this ink was made into Comparative Example 2.

[(C) Inkjet Recording]

Using the ink jet printer (manufactured by Canon Co., Ltd., trade name: PIXUS ^RTM ip7230), various inks prepared by the above Examples 5 to 8 and Comparative Examples 1 and 2 were applied to 2 kinds of glossy papers (spraying). Ink-jet recording was performed on the ink-based paper for the printing density (Dy value) test and chroma (C* value) test. In the case of inkjet recording, an image pattern is produced in such a manner that a reflection density can be obtained by a plurality of stages of gradation, and a recorded matter having a yellow gradation is obtained. The obtained recorded matter was used as a test piece, and various tests were performed.

Glossy Paper 1: Made by Canon Co., Ltd., trade name: Canon Photo Paper. Platinum Grade (PT-201).

Glossy paper 2: manufactured by SEIKO EPSON Co., Ltd., trade name: Photo Paper CRISPIA.

The chroma (C* value) and the reflection density (Dy value) are measured at the highest level. The color measurement system and the reflection density were measured using a color measurement system (trade name: SpectroEye ^RTM , manufactured by X-Right Co., Ltd.). The color measurement was carried out under the conditions of a concentration standard of DIN (German Industrial Standard), a viewing angle of 2 degrees, and a light source D50.

Various test methods for recording images and evaluation methods for test results are as follows.

[(D) Print density test]

The yellow print density (Dy value) was measured by the above-described colorimetric system for the portion of the gradation in which the reflection density was the highest in each test piece. The results are shown in Tables 10 and 11 below.

As is clear from the results of Tables 10 and 11, in the yellow print density test (Dy value), the examples showed superior results compared to the comparative examples, and particularly excellent results were exhibited on the glossy paper 2.

[(E) Saturation Test]

The yellow chroma (C* value) was measured by the above-described colorimetric system for the portion of the gradation in which the reflection density was the highest in each test piece. The results are shown in Tables 12 and 13 below.

From the results of Tables 12 and 13, it was found that in the chroma (C* value), the examples showed excellent results in comparison with the comparative examples.

Therefore, it is understood that the water-soluble azo compound of the present invention or a salt thereof, and the ink composition of the present invention containing the compound have a high-definition hue compared with the conventional dye, and the yellow print density value is high. Excellent color rendering.

[Industrial availability]

The water-soluble azo compound of the present invention or a salt thereof of the present invention as a yellow pigment, and the yellow ink composition of the present invention containing the compound or a salt thereof, can obtain coloration such as saturation, brightness, and printing density on glossy paper. Excellent record image. Further, since an alkoxyaniline substituted with a water-soluble substituent such as a sulfo group is used as a substitute for a raw material such as o-methoxyaniline which is used for a known dye, a compound which is produced by decomposition of a dye is small. . Therefore, the compound and the ink composition containing the compound are very useful for various recording applications, particularly for inkjet recording applications.

Claims (19)

An azo compound or a salt thereof is represented by the following formula (1a): In the formula (1a), A ¹ , A ² and T each independently represent a water-soluble substituent, and Q each independently represents a hydrogen atom, a halogen atom, a carboxyl group, an amine methyl sulfonyl group, a sulfo group, an amine sulfonyl group, a hydroxyl group, an amine group. a cyano group, a phosphoric acid group, a nitro group, a decyl group or a C1 to C4 alkyl group (which may be substituted by one or two or more substituents, and the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine carbaryl group, and Sulfo), C1 to C4 alkoxy (may also be substituted by 1 or more substituents, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group), a C1 to C4 alkane a sulfo group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group), and a C1 to C4 alkylthio group (may also be one) Or substituted with two or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, an aminomethyl group, and a sulfo group, and a C1 to C4 alkylamino group (which may also be substituted by one or two or more substituents) And the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine mercapto group, and a sulfo group, or a guanamine group; each R independently represents a hydrogen atom, a halogen atom, an amine carbaryl group, an amine sulfonyl group, a hydroxyl group, an amine Base, cyano, nitro Mercapto group, C1~C4 alkyl group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an aminomethyl group), and a C1 to C4 alkoxy group (may also be 1) Or a substituent substituted with two or more substituents selected from a hydroxyl group and an aminomethyl sulfonyl group, and a C1 to C4 alkyl sulfo group (may be substituted by one or two or more substituents, and the substituent is Selected from a hydroxyl group and an amine methyl sulfhydryl group, a C1 to C4 alkylthio group (may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an amine methyl group), a C1 to C4 alkane An amine group (which may also be substituted by one or two or more substituents, and the substituent is selected from a hydroxyl group and an amine mercapto group) or a guanamine group; y represents 0 or 1, and z represents 0 or 1, but y+z=1, x represents an integer of 2 to 4, and a and b represent substitution positions of A ¹ , A ² or R. The azo compound or a salt thereof according to claim 1, wherein in the formula (1a), x is 3. The azo compound or a salt thereof according to claim 1 or claim 2, wherein, in the formula (1a), the substitution position of A ¹ is a, and the substitution position of A ² or R is b. The azo compound or a salt thereof according to any one of claims 1 to 3, wherein, in the formula (1a), A ¹ and/or A ² is a sulfo group. The azo according to any one of claim 1 to claim 4 A compound or a salt thereof, wherein, in the formula (1a), T is a sulfo group or a carboxyl group. The azo compound or a salt thereof according to any one of claims 1 to 5, wherein, in the formula (1a), R is a chlorine atom or a methoxy group. The azo compound or a salt thereof according to any one of the preceding claims, wherein, in the formula (1a), Q is a chlorine atom or a bromine atom. The azo compound or a salt thereof according to claim 1, wherein, in the formula (1a), x is 3, the substitution position of A ¹ is a, and the substitution position of A ² or R is b, A ¹ and/or A ² is a sulfo group. The azo compound or a salt thereof according to claim 1, wherein, in the formula (1a), x is 3, the substitution position of A ¹ is a, and the substitution position of A ² or R is b, A ¹ and/or A ² is a sulfo group, R is a chlorine atom or a methoxy group, T is a sulfo group or a carboxyl group, and Q is a chlorine atom. An ink composition containing the azo compound according to any one of Claims 1 to 9 or a salt thereof. The ink composition according to claim 10, which further contains a water-soluble organic solvent. An ink composition as claimed in claim 10 or claim 11, which is used for ink jet recording. An inkjet recording method using the ink composition according to any one of Claims 10 to 12 as an ink, causing ink droplets of the ink to be ejected according to a recording signal and attached to a material to be recorded for recording. . The inkjet recording method according to claim 13, wherein the material to be recorded is a sheet for information transmission. The ink jet recording method according to claim 14, wherein the sheet for information transfer is plain paper or a sheet having an ink receiving layer, and the ink receiving layer contains a porous white inorganic material. A coloring body which is colored by any one of the following: (a) the azo compound according to any one of claims 1 to 9 or a salt thereof; (b) an ink composition, The ink composition contains the azo compound according to any one of Claims 1 to 9 or a salt thereof; or, (c) an ink composition containing any one of Claim 1 to Claim 9 An azo compound or a salt thereof, and a water-soluble organic solvent. A coloring body which is colored by the inkjet recording method according to any one of Claims 13 to 15. An ink jet printer loaded with a container containing the ink composition as claimed in claim 10 or claim 11. A method of producing the azo compound according to any one of Claims 1 to 9 or a salt thereof, and the method comprising the step of reacting a compound represented by the following formula (5a) with a haloformate condensation; In the formula (5a), A ¹ , A ² , T, Q, R, x, y, z, a and b have the same meanings as those represented by the above formula (1a).