TW201235418A - Water-soluble azo compound, salt thereof, ink composition, and colored body - Google Patents

Abstract

The purpose of the present invention is to provide: a water-soluble yellow pigment (compound) exerting high water solubility and coloring properties, and exhibiting excellent color saturation on recorded images; and a yellow ink composition for various recordings, particularly inkjet recording, the yellow ink composition containing the aforementioned yellow pigment (compound). A water-soluble azo compound represented by formula (1) or a salt of the water-soluble azo compound is used to obtain an ink composition exerting high coloring properties, various fastness properties for recorded products, and storage stability of recorded images, and having the color saturation and hue appropriate for inkjet recording. In formula (1), x represents an integer between 2 and 4, and group (A) represents an amino group represented by one of the formulae from among formula (2) to formula (6). In formula (2), y represents an integer between 1 and 5. In formula (3), w represents an integer between 2 and 6. In formula (4), m represents 1 or 2. In formula (5), n represents an integer between 0 and 2, and Z represents a hydrogen atom, a carboxy group, or a sulfo group. In formula (6), R represents a hydrogen atom or a sulfo group.

Description

201235418 VI. [Technical Field] The present invention relates to a water-soluble bisazo compound or a salt thereof, an ink composition containing the same, or a coloring composition thereof It is made into a color body. ---- [Prior Art] Among various color recording methods, various ink ejection methods have been developed as a recording method by an ink jet printer as one of representative methods. These are all caused by the droplets (ink droplets) of the ink being produced and attached to the I-recorded material (paper, film, cloth, etc.), and the method is performed by the recording head and the recorded material. It is not in direct contact, so it is less quiet and quieter. In addition, the financial method is rapidly becoming popular in recent years due to its characteristics of being easy to be miniaturized and high-speed, and it is expected to increase significantly in the future. X is ink such as a pen or a signature pen, and ink for inkjet recording. - A type of ink is used, which is obtained by dissolving a water-soluble dye (dye) in an aqueous medium. In these aqueous inks, a water-soluble organic solvent is generally added to prevent the ink from clogging at the tip of the pen or the nozzle of the ink nozzle. These inks are required to have a performance in which a recording image having a sufficient concentration can be obtained, clogging of the pen line nozzle is not caused, drying property on the material to be recorded is good, material is small, and storage technique is excellent. The clogging of the inkjet nozzle is mostly caused by the fact that in the vicinity of the nozzle 201235418, the water in the ink evaporates faster than other solvents or additives, and forms a composition state in which the water is less and the solvent or the additive is more. Will solidify and precipitate. Therefore, one of the most important required properties is that solids are not easily precipitated even when formed into a state in which the amount of moisture in the ink is small. According to this reason, the solubility of the solvent or the additive is high, and it is also a property required for the pigment. In addition, the method of solving the higher pigment of the nozzle-blocking type is solved. By using a pigment having a higher printing density, it is possible to maintain both the conventional printing density and the ink content of the ink. In this case, not only the pigment is not easily precipitated, but also it is advantageous in terms of cost, and it is desired to develop a pigment having a high printing density. However, 'when the color of the computer is recorded in color by the inkjet printer', the image or text information on the device is used to generally use subtractive color mixing by yellow (7), magenta ( M), cyan (c), ::, color (K) four colors of ink are used to display the recording image in color. In order to reduce the color mixed image, the CRT (as much as possible) Cloth I) The additive color η image obtained by red (8), green (6), and blue (8) is faithfully reproduced, and it is expected that the respective pigments used in the ink, π M thereof, c' has a hue close to the standard color and is distinct. Here, the so-called sharpness, the general low-pitched W private eight has a chroma. When using the three primary colors of Y, Μ, and c with low chroma, the date can be narrowed, and the color gamut of the gamut to be revealed is expected to develop a high chroma + dead knife. Therefore, the color, and the color Pigment ink. In addition, the performance of the ink is required. The concentration of the recorded image is high, and (4), (4) is stored as a stable, and the image is excellent in water resistance, moisture resistance, light resistance, and gas resistance of 201235418. Here, the term "gas resistance" refers to resistance to a phenomenon in which an oxidizing gas (also referred to as an oxidizing gas) existing in the air is recorded on a material to be recorded or recorded. The pigment (dye) reacts to change/fade the recorded image. It is generally considered that 'the oxidizing gas is especially ozone gas, in order to promote the inkjet recording image--variation-factor fading-present-image-((4)----------------------------------- - Spraying - Ink - Recording - It is a peculiar phenomenon, so it is an important technical problem in the field to improve ozone resistance. In recent years, inkjet technology has developed, so inkjet recording (printing) The speed is significantly improved. Therefore, as with the laser printer using the electronic toner, the paper is printed on the plain paper as the main use in the office environment, and the market trend tends to use the inkjet printer. Machine. Inkjet printer system> has the following advantages: The type of recording paper is not selected, and the price of the printer itself is cheap, especially in the SOHO (Small Office Home 〇fflCe) family. In the medium-sized office environment, it is becoming more and more popular. When using an inkjet printer in such a use for printing on plain paper, the color and color (printing) are more important in the quality of the printed matter required for printing. Concentration, and water |§ h & For the purpose of satisfying these properties, the use of pigment inks and soils has been proposed. However, 'pigment inks are not soluble in inks because the pigments do not form into a solution state. For the ink in the dispersed state, =: the ink is used for inkjet recording right. 'The problem of the ink itself and the nozzle clogging of the recording head may occur. In addition, when the pigment ink is used, ^ There is also a problem with the rubbing property. When dye ink is used, it is generally considered that it is less prone to the problem of the above-mentioned problems, but it is obviously worse than the pigment ink in terms of water resistance 201235418, so it is strongly expected to target In this case, the dye ink is different from the pigment ink, and the dye which is recorded on the surface of the plain paper by the field ink is more quickly penetrated toward the back side of the paper, and as a result, the color density is lowered. One of the methods for obtaining an inkjet image of a photo enamel has a method of being -recorded-recorded-material------------------ - the ink-receiving layer, which is provided in the same manner as the one-head, often contains a porous white inorganic substance to accelerate ink drying and reduce pigmentation under high image quality. However, especially in such a recorded material It is possible to significantly observe the above-mentioned change/fading caused by ozone gas. Since the recent popularity of digital cameras and color printers, images obtained by digital cameras and the like are printed in the form of photo enamel in the home. Opportunities have also increased, so the above-mentioned recording image change/fading caused by oxidizing gas has become a problem. Compared with the other three primary colors of magenta and cyan, 'about yellow pigments have been proposed to have light resistance and good A pigment which is resistant to oxidizing gases. However, it has not been possible to obtain a yellow pigment and a yellow ink which have been employed in the ink jet 5, which sufficiently satisfy the high sharpness and various firmness as required by the market. A conventional yellow pigment for inkjet which is excellent in water solubility and vividness is, for example, C.I. (C〇l〇r Index, color index) Direct Yellow 132. Therefore, since the development of yellow pigments for inkjet recording has been carried out in recent years, a plurality of highly azo-based dyes have been proposed. Patent Document 1 discloses a yellow water-soluble azo compound which is highly soluble in water and has moisture resistance and light resistance. Patent Document 2 discloses a yellow water-soluble azo compound which is highly soluble in water in 201235418 and has moisture resistance, ozone gas resistance, and light resistance. Patent Document 3 discloses that it is not a rare one; recognizes I» Ι·Λ, - steam color water > gluten azo compound, which has high solubility in water '. and has 妍, how, # uk , , , , Humidity, water resistance, ozone gas resistance, and light resistance. (4) Document 4 reveals a yellow water-soluble azo compound which is ----^ and lightfast. [Prior Art Document] (Patent Document) Patent Document 1: U.S. Patent No. 6,867,286, Patent Document 2: JP-A-2006452244, Patent Document 3: International Publication No. 2008/053776 Patent Document 4: JP-A-2009-263514 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a water-soluble yellow pigment (compound) and a yellow ink composition containing the yellow pigment, which has high solubility in water. Moreover, it has high color rendering property (printing density) of the recorded image and excellent chromaness. The yellow ink composition is used for various recordings, particularly for inkjet recording. [Means for Solving the Problems] After the inventors of the present invention have made efforts to solve the above problems, it is found that a water-soluble azo compound represented by a specific formula and an ink composition containing the water-soluble azo compound can be solved. The above problems have been completed by the present invention. In other words, the invention relates to the following. 1) 'species-water-soluble-sex-even-1^7"-------------------------------------- :

H03S(CH2)x0 0(CH2)xS03H

Cl—^^-Ν=Ν- ho3s" -ΝγΝγΝ-^3_Ν=Ν~^-^_°, (1)

ΝγΝ S03H (wherein χ represents an integer of 2 to 4, and the hydrazine represents an amine group represented by any one of the following formulas (2) to (6))

-n(H (2) (CH2)y-C02H (in the formula U), y represents an integer from 1 to 5) Ή (3) v(CH2)w-〇H (-Hh (k, in equation (3)) mC〇2H (in the formula (4), jn represents 1 or 2) (0Η2) π-〇^, w represents an integer of 2 to 6) (4) (5) ζ (in the formula (5), η represents 0~ An integer of 2, Ζ represents a hydrogen atom, a carboxyl group, or a 201235418 contig)

(6) (In the formula (6), R represents a hydrogen atom or a sulfo group 2), as described above, the -) valence water-soluble one-coupling or -1 - in the above formula (1), X For .3. Guaqi - Zhongyi, one at 3)

The water-soluble azo compound or a salt thereof according to the above 1), wherein the water-soluble azo compound represented by the formula (1) is "two

H03S(CH2)30 〇(ch2)3so3h ^ (7} ^ ^

U so3h 'yVN-0-N=N-Q-c, (7 h2 - co2h 4) An ink composition' containing the water-soluble azo compound or a salt thereof as described in the above 1) to 3). 5) The ink composition according to the above 4), wherein the nickname is Hegu* Ϊ organic solvent. Water-soluble 6) The ink composition according to the above 4), which is an ink jet. Use green. 9 7) 201235418 kinds of inkjet. In the recording method, the ink composition according to the above 4) is used as the ink, and the ink droplets of the ink are ejected on the recording material according to the recording signal to be recorded. 8) The inkjet recording method according to the above 7), wherein the said recording material is a capital-information-transmission----- 9) inkjet according to the above 8) In the recording method, 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 substance. 10) A coloring body which is colored by any one of the following: (a) a water-soluble azo compound according to the above 1) or a salt thereof; (b) containing as described above) An ink composition of a water-soluble azo compound or a salt thereof; and (a composition comprising the water-soluble azo compound according to the above 1) or a salt thereof and an ink composition of a water-soluble organic solvent. Π) A color body formed by the ink jet recording method as described in the above 7). 12) An ink jet printer which is filled with a container containing the ink composition as described in 4) above. 201235418 [Efficacy] The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof has the following characteristics: high solubility in water, and production of the present compound or a salt thereof In the process of the ink composition of the invention, for example, the membrane filter is excellent in properties. In addition, compared with the image obtained by using the conventional compound, by containing the hair, the chemical-combination-text------------ The resulting image has a better print density and chroma. In this case, the water-soluble azo compound of the present invention or a salt thereof according to the above formula (1) and the ink composition containing the water-soluble azo compound or a salt thereof are very useful for various inks for recording, in particular, It is often useful for inks for inkjet recording. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The water-soluble azo compound or salt of the present invention represented by the above formula (1) is a water-soluble yellow pigment. In the present specification, the ionic group, the reduced or the like acidic functional group is expressed in the form of a free acid, unless otherwise specified. In addition, as described above, the present invention contains both a soluble azo compound represented by the above formula (1) and a salt of the compound, but it is often complicated to describe both of them as "a compound or a salt thereof". Therefore, for the sake of convenience, unless otherwise specified, "the (water-soluble azo) compound of the present invention or a salt thereof" is included, and the following is simply described as "the present invention (water: 201235418 azo Mb» The compound of the present invention is an integer of 2 to 4, preferably 3 (1). In the above formula (1), χ is an amine group of the group A in the above formula (1). Wherein, the above formula '^, the above formula (7) ~ (6) is - shown as - Jiayi.--_, y represents an integer from 1 to 5, to ! in the above formula (3), you table ~ ~ '- ... 2 to 6 integers, preferably 2. Bu, in the above formula (4), m table _, the table is not 1 or 2, preferably 2. ^ Z represents a hydrogen atom 1 base, or performance The base is preferably a furnace. η represents an integer of 〜2, preferably i. In the formula (6), 'R represents a hydrogen atom or a sulfo group, and the base A is represented by the above formula (7) or (7). The amine group is preferably 'the amine group which is not represented by the above formula (7). 4 Formula (2) Among the above groups A, z, R, m ^ y, the combination is preferable, and the combination is preferred. The compound is better. The combination of the best and the better is also excellent. In the U phase, the compound of the present invention represented by the above formula (1) represented by the above formula (7) can be produced, for example, in the following manner. Further, the base which is appropriately used in the following formulas (ΑΑ) to (1) A, z, R,...

m, n, w, X and y ' are the same meanings as the radicals A, Z, R R, m, n, . , 乂 and 丫 in the above formula (1), respectively. After obtaining a compound represented by the following formula (AA) by a conventional method using a 2-aminophenol of a commercially available product, the following formula (AA) is used using sodium hydrogen sulfite and formalin. The compound was converted into a methyl 12 201235418 -ω-sulfonic acid derivative represented by the following formula (B). Then, the 5-amino-2-chlorobenzenesulfonic acid of the following formula (c) is diazotized by a conventional method, and then reacted at a reaction temperature of 15 ° C and a pH of 2 to 4 to cause The 0J-sulfonic acid derivative obtained by the following formula (B) obtained by the coupling reaction is subjected to a coupling reaction, and then a hydrolysis reaction is carried out at a reaction temperature of 80 to 95 t and a pH of 10.5 to 11.5, whereby the following formula (1)) is obtained. - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Then, at a reaction temperature of 15 to 451 and a pH of 5 to 8, a compound represented by the above formula (D) (2 equivalents) and a trimeric cyanogen halide (1 equivalent), for example, a trimer gas

Cyanide (1 equivalent) is condensed, thereby obtaining a compound represented by the following formula (E): H03S(CH2)x9 0(CH2)xS03H

Cl

ci-Q--n=n ho3s^ (E) and 'by any of the following formulas (F) to (J) under the conditions of a reaction temperature of 75 to 9 ° C and a pH of 7 to 9 The amine shown is substituted for the gas atom on the tHazine ring in the compound of the above formula (Ε) obtained, that is, 13 201235418, which is sufficient to obtain the compound of the present invention represented by the above formula (1).

, (CH2)y-C02H (F)

"(CH2)w-〇H (G)

Co2h (CH2)mC02H (H) H~NH, (CH2)nQ^ (1) co2h h-b4h-^ (j) R Specific examples of the amine represented by the above formula (F) include, for example, glycine and amphetamine酉文 4-Aminobutyric acid, 5-aminolevulinic acid, 6-aminoglycol, etc. Specific examples of the amine represented by the above formula (9) include, for example, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, and 6-aminohexanol. Specific examples of the amine represented by the above formula (H) include aspartic acid and cholamine. Specific examples of the amine of the above formula (1) include aniline, methylamine, phenethylamine, 4-aminomethylbenzoic acid, 4-aminomethylbenzoic acid, 2-aminobenzoic acid, and 3 - aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzoic acid, amine-aminobenzoic acid, 4-aminobenzoic acid, and the like. Specific examples of the amine represented by the above formula (J) (4-thylphenyl)glycine and the like. For example, phenylglycine and a specific example of the compound of the present invention represented by the above formula (1) are shown in the following Tables 35, pp pps to 6, but the present invention is not limited to these specific examples. Furthermore,

In the following table, the base A, Z, R, m, n, w, Uy_M in the above formula (1) or in the base A, z, R, m, n « K " ^" ..., parent and ^ compound number 1 Specific examples of the compound of the group 7 to the amino group represented by the above formula (2), the group of the compound No. 8 to 12, a λ } 诂 4, and the amine of the above formula (3): = system, compound number - base A is a specific example of the above formula, 'amine compound, compound number 15~

Specific examples of the compound of the amine group which is not the base of the face A 25 of the above formula (5), the base aa compound No. 27 of the compound No. 27, the earth A is an amine group represented by the above formula (6) Compounding 夂 Specific example 0 15 201235418 [Table i]

Compound No. Structure X ywm η 1 R 1 2 1 H03S(CH2)20 0(CH2)2S03H H03s ΝγΝ S03H HW ch2-co2h 2 3 1 H03S(CH2)3〇O(CH2)3S03H H03S ΝγΝ S03H HN ch2- Co2h 3 4 1 ho3s(ch2)4? ?(ch2>4so3h Ch^-N4^4!x^N-0-^-Q-CI H03S ΝγΝ S03H HN ch2-co2h 4 3 2 H03S(CH2)30 〇( CH2)3S03H ci-〇hw^4J^i^yn-Qh^nQ-ci ho3s N^N so3h HW, (ch2)2-co2h 5 3 3 ho3s(ch2)3o 0(CH2)3SO3H ho3s n>^n So3h HN , (CH2)rC02H 16 201235418 [Table 2] Compound number structure X y W η Ζ R 6 3 4 H03S(CH2)3〇0(CH2)3S03H H03S ΝγΝ S03H HN , (ch2)4-co2h 7 3 5 H03S(CH2)30 0(CH2)3S03H ho3s n^n so3h HN ,(CH2>rC02H 8 3 2 H03S(CH2)3〇0(CH2)3S03H H03S ΝγΝ S03H HN X(CH2)2-〇H 9 3 3 H03S(CH2)3〇0(CH2)3S03H H03 Plant ΝγΝ S03H HN X(CH2)3-〇H 10 3 4 H03S(CH2)3〇0(CH2)3S03H H03s ΝγΝ S03H HN ,(ch2)4- Oh 17 201235418 [Table 3] Compound number structure X y ta η 1 R 11 3 5 H03S(CH2)3〇0(CH2)3S03H HO3S ΝγΝ S03H HN , (ch2)5oh 12 3 6 H03S(CH2)30 0(CH2)3S03H ch^n=n^4L^丫ί^^·Ν=Ν"〇«α H03s ^ΙγΝ S03H HM , (ch2)6-oh 13 3 1 H03S( CH2)30 0(CH2)3S03H H03S ΝγΝ S03H HNy-C02H ch2co2h 14 3 2 H03S(CH2)3〇0(CH2)3S03H H03s ΝγΝ S03H hnv-co2h (0H2)2C02H 15 3 0 Η H03S(CH2)30 0 ( CH2)3S03H H03S ΝγΝ S03H ΗΝΌ 18 201235418 [Table 4] Compound braided structure X y D η 1 R 16 3 1 Η H03S(CH2)3〇c H03S ΝγΝ HN ch2- )(CH2)3S03H 3^N"Q ^ci so3h 0 17 3 2 Η ho3s(ch2)3o O(CH2)3S03H H03s ΝγΝ ^03H 18 3 1 S03H H03S(CH2>3〇c H03s N-fN HN CH2"· >(CH2)3S03H 3^= N"Q«a so3H —^^-S03H 19 3 0 S03H H03S(CH2)30 0(CH2)3S03H H03S ΝγΝ S03H h〇:sX5 20 3 0 S03H H03S(CH2)30 H03S ΝγΝ ΗΝΰ so; D(CH2) 3S03H Qn=^Qc* so3h 19 201235418 [Table 5]

Compound number station type X y W η η ζ R 21 3 0 S03H H03S(CH2)3〇O(CH2)3S03H H03s S03H 22 3 0 C02H H03S(CH2)30 O(CH2)3S03H H03S N-fN S03H H: ^0 23 3 0 C02H H03S(CH2)30 0(CH2)3S〇3H HOgS ΝγΝ S03H HN« COzH 24 3 0 C02H H03S(CH2)3〇0(CH2)3S03H ci~Q~n=n~^3ynyR^ ~n=n~Q~ci H03S ~N SO3H 25 3 1 C02H H03S(CH2)30 0(CH2)3S03H H03S N^N SO3H, H2-〇-C〇2H 20 201235418 [Table 6]

In the formula (8), 'z~Z each independently represents a hydrogen atom, a hydrazine 1 to C4 alkyl group, a transbasic C1 to C4 alkyl group, or a hydroxy Ci~C4 alkoxy group C1 to C4, and a Zi~z4 At least one of them is a group other than a hydrogen atom. Examples of the above C1 to C4 alkyl groups in 'Z1 to z4' herein include a methyl group and an ethyl group. Similarly, examples of the above-mentioned hydroxy c丨 to C4 alkyl group include hydroxy fluorenyl group, hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 21 201235418 4-hydroxybutyl group, and 3-hydroxybutyl group. , 2-hydroxybutyl and the like. Similarly, examples of the above-mentioned hydroxy C1 to C4 alkoxy C1 to C4 alkyl group include a hydroxyethoxymethyl group, a 2-transethoxyethyl group, a 3-(transethoxymethyl)propyl group, and 3_ (via ethoxy) butyl, 2-(hydroxyethoxy)butyl and the like. Among the above salts, preferred are alkali metal salts such as sodium salt, potassium salt and lithium salt; salts of monoethanolamine, salts of diethanolamine, salts of triethanolamine, salts of monoisopropanolamine, and diisopropyl ester. An organic quaternary ammonium salt such as a salt of an alcoholamine or a salt of a triisopropanolamine; an ammonium salt or the like. Among these, a lithium salt, a sodium salt and an ammonium salt are preferred. The salt or free acid of the compound represented by the above formula (1) can be easily obtained by the following method or the like as is well known to those skilled in the art. By separating the precipitated solid by filtration, a wet cake of a sodium salt or the like of the compound of the above formula (1) can be obtained, and the solid is precipitated by the following method, for example, a compound represented by the above formula (1) In the reaction solution after the end of the last step in the synthesis reaction, or in an aqueous solution containing a salt of the compound of the above formula (1), or the like, for example, acetone or a method of water-soluble organic solvent of (CM) (IV); Nalai is the ingredient of salting out. Further, 'the free acid of the compound represented by the above formula (1) can also be obtained by appropriately adding the acid obtained by dissolving the obtained salt of the (Na) cake in water, adding an acid such as hydrochloric acid, and separating the precipitated solid by hydrazine. Or a part of the compound represented by the above formula (1) is a mixture of a free acid and a sodium salt of a sodium salt. In addition, it is sufficient to appropriately adjust the pH to, for example, by adding the obtained sodium salt wet cake or its dry solid to the ruler and then adding an ammonium salt such as ammonium chloride and adding an acid such as hydrochloric acid. After pH 1 to 3, the precipitated solid 22 is isolated by filtration. 201235418 The ammonium salt of the compound represented by the above formula (1) is obtained. By appropriately adjusting the amount of y, the amount of vaporized ammonium or/and the pH, it is also possible to obtain a mixture of the money salt and the sodium salt of the compound of the formula (1); the above formula (1) a mixture of a free acid and an ammonium salt, and the like. In addition, as described later, the reaction solution after the completion of the above reaction is added with mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to directly obtain the free acid, which is exaggerated by the compound represented by the above formula (1). In the wet filtration of acid, the following compounds are added to produce salts, and it is also possible to obtain a salt, a lithium salt, a salt, a graded muscle, etc. corresponding to the added compound. Oxidation and dehydration; hydrogen peroxide; ammonia; an organic quaternary hydroxide represented by the above formula (8). By limiting the molar amount of the above-mentioned hydroxide or the like with respect to the molar amount of the free acid, it is also possible to prepare, for example, a mixed salt of a clock salt and a nano salt; and a chain salt, a sodium salt, and a salt salt. Mix salt and so on. The salt of the compound represented by the above formula (1) may be changed depending on the type of the salt: physical properties such as solubility or the performance of the ink when used as an ink. Therefore, it is preferred to select the type of salt depending on the performance of the target ink or the like. The compound of the present invention represented by the above formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid after completion of the reaction, and can be acidic water such as water or hydrochloric acid. = washing: etc. to remove the inorganic salt contained in the form of impurities (n = and the free acid of the compound of the present invention is as described above == 研' has a solid, in water with the desired inorganic base or has 23 201235418 A solution for the salt of the corresponding compound is obtained by a method of "processing". The inorganic base may, for example, be a hydroxide of an alkali metal such as lithium hydroxide, sodium hydroxide or potassium hydroxide; or a base such as lithium carbonate, sodium carbonate or potassium carbonate. A metal carbonate; a hydroxide (ammonia water), etc. An example of the organic base is, for example, an organic amine corresponding to a quaternary ammonium compound represented by the above formula (8), for example, an alkylene such as diethanolamine or triethanolamine. The alcohol amine or the like is not limited thereto. The compound of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and is suitable for producing inks for writing and inks for inkjet recording. For example, the above formula (1) The reaction solution of the compound of the present invention is shown, and the reaction liquid after the final step can also be directly used for the production of the ink composition of the present invention. However, it can also be carried out by a method such as the above method or spray drying. After the reaction solution or the like is dried and the compound is isolated, the obtained compound is processed into an ink composition. The ink composition of the present invention is obtained by dissolving the compound represented by the above formula (1): water or water and water-soluble. A mixed solution (3) in which an organic solvent (an organic solvent capable of mixing with water) is mixed is referred to as an aqueous medium, and if necessary, an ink preparation agent is added. When the ink composition is used as an ink jet printer In the case of ink, it is preferred to use a content of the following inorganic impurities: a chloride which is a cation such as sodium chloride; a sulfate such as sodium sulfate 2 which is contained in the form of impurities. The above-mentioned:) The total mass of the compound which is not used, for example, the content of sodium chloride and sodium sulfate is less than or equal to the mass%. The lower limit value is % by mass, that is, the detection limit of the detector. . To shock, can be exemplified as follows: Method of the compound machine itself, as the abundance of a reverse osmosis membrane by methods known in the s;

'S 24 201235418 Add a dry or wet cake of the compound of the present month to a water-soluble organic solvent such as a propyl or a-C4 alcohol (for example, methanol, ethanol, isopropanol, etc.) or water-cooling of water In the organic solvent, a method of performing suspension purification or crystallization, etc., may be carried out by such a method. In the total mass of the ink composition, the ink composition of the present invention has a compound represented by the above formula (1) in an amount of 0.1 to 20% by mass, preferably 8% by mass, and preferably 2 to 8% by mass. The ink composition of the present invention suitably contains a water-soluble organic solvent and an ink preparation agent, which is prepared by using water as a medium and which does not impair the efficacy of the present invention. The water-soluble organic solvent sometimes has the following effects: dissolving the dye. preventing the composition from drying (maintaining a wet state); adjusting the viscosity of the composition; promoting the penetration of the pigment into the recorded material; adjusting the surface tension of the composition; It is preferable to contain a water-soluble organic solvent in the ink composition of the present invention. The ink preparation agent may, for example, be a preservative antifungal agent, a pH adjuster agent, an anti-caries agent, an ultraviolet absorber, a viscosity adjuster, a dye dissolving agent, an anti-fading agent, a surface tension adjusting agent, an antifoaming agent, etc. Additives. The content of the initiator of the ink composition of the present invention is preferably 〇~60 followed by; in the 'water bath organic solvent „ A1 罝/〇 is preferably 10 to 50% by mass, and the ink preparation is preferably used. ～20质量%, egg, 罝/0 is preferably 〇15% by mass. In the ink composition of the formula, the organic solvent other than the compound represented by the above formula (1) and the ink preparation agent are water. The water-soluble organic solvent may, for example, be an alcohol, 25 201235418 isopropanol, n-butyl hydrazine, isobutanol, secondary butanol, tertiary butanol, or the like, a C1 to c4 alcohol, a methyl-methylcarbamide, Indoleamines such as hydrazine, hydrazine-dimercaptoacetamide; 2-pyrrolidone, '~ fluorenyl-2-pyrrolidone, hydroxyethyl-2-pyrrole _, 1'3_-mercaptoimidazole _2__, dimethyl hexahydropyrimidinone and other heterocyclic rings " acetone, methyl ethyl ketone, 2 曱 _2 2 _ hydroxypenta-4 ketone and other ketones or sun alcohols 'tetrahydro flurane, Two-dimensional burning (dioxane) and other ringing shout; ethylene glycol, 1,2-propylene glycol, 1, 2, 3-propanediol, indane butane, ls4_ butanediol, Lb-hexa-G glycol, triethylene Alcohol, tetraethylene glycol, Propylene glycol 'polyethyl rP%-alcohol, thiodiglycol, etc., mono-, oligo or polyalkylene glycol having a C2~C6 alkylene unit or thioethylene glycol; -1,2,6-triol and other polyols (preferably triol); ethylene glycol mono-diyl group, ethylene glycol monoethyl (tetra), diethylene glycol monomethyl bond, 'diethylene glycol Monoethyl sulphate diethylene glycol monobutyl hydrazine (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl sulphate and other polyols ci ~ C4 monoalkane, Γ-butyl vinegar; dimethyl sulfoxime dimethyl hydrazide (dimethylsuif 〇 x ide), etc. Further, the water-soluble organic solvent also contains a substance n ... which is solid at room temperature like, for example, trimethylolpropane Rfq, the substance or the like is still water-soluble, and the aqueous solution containing a substance or the like does not exhibit the same properties as the water-soluble organic solvent, and the same effect is expected to be used. Therefore, in the present specification In the case of a horse, it is convenient, as long as it is such a solid substance, it can be expected to use the same effect as the upper one, that is, it is contained in Within the scope of a soluble organic solvent. Preferred as the above water-soluble organic solvent: isopropyl alcohol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, di-intermediate-alcohol, 2-n-butyl ketone , 26 201235418 Hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, trimethylolpropane, and butyl carbitol, isopropanol, glycerol, diethylene glycol, 2 Pyrrolidone, N-methyl-2-pyrrolidone, and butyl carbitol are preferred. These water-soluble organic solvents can be used singly or in combination. The above antiseptic and antifungal agent can be, for example, an organic sulfur system. , organic nitrogen sulfur, organic halogen, haloallyl fluorene, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8-hydroxyquinoline , isothiazoline system, dithiol system, pyridine oxide nitropropane system, organotin system, phenolic quaternary ammonium salt system, three tillage system, thiadiazine system, hydrazine Aniide, adamantane dithiocarbamate, bromoindanene, bromoacetate, inorganic Etc. based compound. The organic compound may, for example, be sodium pentaphenolate, and the acridine oxide compound may, for example, be a 2-sodium pyridinium-oxime oxide sodium salt. The isothiazolidine-based compound may, for example, be hydrazine, 2_benziso-α-sedrin-1 ketone 2-n-octyl-4-isoindole. Sit, 5_gas_2_methyl_4_ sigh sin | ketone, 5-gas-2-methyl _4_isothiazoline _3 ketone magnesium chloride, % qi methyl oxime spit _ 3 'chlorination, 2 · f base _4 · isoindole _3_ 嗣 gasification and so on. Other antiseptic and antifungal agents include, for example, sodium acetate

Arch 〇hemicals . 51 , ,, , Pr〇xe;: GXL(S) or Proxei_XL_2(8), etc. Furthermore, the term "RTM" as used in this specification means a registered trademark. The pH adjuster can be used to control the pH of the ink to a range of, for example, 6. 〇 to 11 为了 for the purpose of improving the storage stability of the ink. For example, diethylamine, anthranol such as lithium hydroxide-alcoholamine, or an alkali ammonium hydroxide such as potassium hydroxide; lithium carbonate, magnetic cabin hydroxide, m sodium, carbon, etc. Equivalent sulfonic acid, etc. _ <Anti-hurricane, the chelating agent may, for example, be bis-g-amine tetraacetic acid disodium, sodium nitrite, sodium hexyl ethylenediamine triacetate ^- ethane ^ diacetate sodium, and the like. Examples of the ethylene diamine pentaacetic acid sodium and urinary rust inhibitors include: acid r sulfite salts 'sodium thiosulfate, ammonium thioglycolate, nitrous acid-li; μ., isopropylammonium isopropyl, Pentaerythritol tetranitrate vinegar, dicyclohexylammonium nitrite, and the like. The ultraviolet absorber may, for example, be a diphenyl (tetra) compound or a benzotriene. The squat compound, the cinnamic acid compound 'three-till compound stilbene compound, and the like. Further, it is also possible to use a compound which is fluorinated by benzopyrene and (10) (4) which absorbs ultraviolet rays and which emits fluorescence, that is, a so-called fluorescent whitening agent. In addition to the water-soluble organic solvent-soluble polymer compound, for example, polyethoxyethanol, a cellulose derivative, a polyamine, a polyimine, or the like may be mentioned. The dye solubilizing agent may, for example, be urea, ε-caprolactam, carbonic acid acetonitrile or the like. Among them, urea is preferred. The anti-fading agent is used for the purpose of improving the preservation of the image. Anti-fading agents can be used: various organic and metal complex anti-fading agents. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, di-oxygen groups, aliquots, anilines, amines, dihydro^(indane), and color 28 201235418 chromane Classes, alkoxylated amines, heterocyclics, and the like. The metal complex compound may, for example, be a nickel complex or a zinc complex. The surface tension adjusting agent may, for example, be a surfactant, and examples thereof include a p-ionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. The anionic surfactant may, for example, be an alkyl sulfocarboxylate, an < olefin sulfonate, a polyoxyethylene alkyl ether acetate, a N-mercapto amino acid, and Its salt, sulphate methyl taurate, sulphate sulphate polysulfate sulphate, sulphur sulphate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, laurel Alcohol sulfate salt, alkylphenol type phosphate, alkyl type phosphate 'alkyl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfo amber Acid salt, etc. The cationic surfactant may, for example, be a 2-vinylpyridine derivative or a poly(4-vinylpyridinium) derivative. The amphoteric surfactant may, for example, be lauryl dimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl_N-hydroxyethyl imidazoline rust betaine, coconut oil fatty guanamine propyl Dimethylaminoacetic acid betaine, polyoctyl polyamine ethylglycine, other U rice saliva derivatives, and the like. The nonionic surfactant may, for example, be polyoxyethylene phenyl phenyl I polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl Ether, polyoxyethylene alkyl ether and other ether systems; polyoxyethylene oleic acid vinegar, polyoxyethylene distearate vinegar, sorbitan laurate, sorbitan monostearate, sorbitan Monooleate, mountain 29 201235418 Ester esters such as sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetradecyl- Acetylene such as 5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimercapto-1-hexyne-3·ol Glycol (alcohol); trade name Surfyn() 1RTM 104 ' SurfynolRTM 82 ' SurfynolRTM 465 > 01fineRTM STG; manufactured by SIGMA-ALDRICH under the trade name TergitolRTM 1 5_s_7. Examples of the antifoaming agent include a sulfuric acid-based compound, a glycerin fatty acid-based compound, a fluorine-based compound, and a ruthenium-based compound. These ink modulating agents can be used singly or in combination. Furthermore, the surface tension of the ink composition of the present invention is usually 25 to 70 mN/m, preferably 25 to 60 mN/m, and the viscosity is adjusted to 30 mPa. s or less, preferably 20 mPa·s or less. good. In the production of the ink composition of the present invention, the order in which the respective agents such as additives are dissolved is not particularly limited. The water used in the preparation of the ink composition is preferably water having less impurities such as ion-exchanged water or distilled water. Further, after the ink composition is prepared as needed, it is precisely filtered using a membrane filter or the like to remove inclusions in the ink composition. In particular, when the ink composition of the present invention is used as the ink for inkjet recording, it is preferred to perform precision filtration. The pore size of the filter used for precision filtration is usually 1 to 〇1 μπι', preferably 0.8 to 0.1 μπι. The ink composition containing the compound of the present invention is suitable for use in the following cases: printing, photocopying, marking, writing 'drawing, printing, or recording (printing)', particularly inkjet recording. Further, the ink composition of the present invention Even if the vicinity of the nozzle of the recording head of the ink jet printer is dry, it is unlikely that solids 201235418 will be precipitated. For this reason, the head jam is unlikely to occur. The method of recording on a material to be recorded by the ink jet recording method of the present invention may be, for example, the following method. In other words, the method is to fill a container filled with the ink composition of the present invention at a predetermined position of the ink jet printer, and after using the ink composition of the present invention as an ink, the ink droplets of the ink are ejected according to the recording signal. And attached to the recorded material for recording. In the ink jet printer, there are printers of the following type, for example, a piezoelectric method using mechanical vibration, a BubMe registered trademark using bubbles generated by heating, and the like. The ink jet recording method of the present invention can be used in any manner. Sometimes, in order to obtain a higher-definition recording image, two inks containing the same pigment are loaded in the inkjet printer. The difference between the two kinds of inks is the content of the dye, and one of the inks is made into a higher-content ink, and the other ink is made into a lower-content ink 7 to be used as an ink set. The ink composition of the present invention can also be fabricated into such an ink set. Further, the ink composition of the present invention may be used in one of the inks of the ink set, and the conventional ink (composition) may be used in the other ink. The ink composition of the present invention may be formed into a yellow ink containing the compound of the present invention and a conventional yellow pigment for the purpose of finely adjusting the hue thereof within a range not inhibiting the effects obtained by the present invention. Things. Further, the compound of the present invention can be used in combination with a magenta dye or a cyan pigment for the purpose of coloring other colors of ink, for example, black ink, or for modulating red ink or green ink. Further, in order to obtain a blue recorded image, the ink composition of the present invention 31 201235418 can be used in combination with the inks of the following colors: magenta, cyan; and green, blue as needed ( Or purple), red, black, etc. At this time, it is only necessary to perform inkjet recording in such a manner that ink of each color is filled in the respective containers +, and the containers are loaded at predetermined positions of the ink jet printer. The material to be recorded used in the inkjet recording method of the present invention may, for example, be a sheet for information transmission such as a paper 1 film; a fiber for fibers and cloth (such as cellulose, Nike, wool, etc.), a substrate for a color filter, or the like. Information transfer sheets are preferred. The sheet for information transfer is not particularly limited, and plain paper can of course be used, or a surface-treated 胄 胄 胄 系 系 系 基材 基材 基材 基材 基材 基材 基材 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Thin material. The ink-receiving layer B has a layer which functions to absorb ink and accelerate drying thereof. The ink receiving layer is provided by, for example, a method of impregnating a cationic polymer with the base material or applying a cationic polymer to the substrate; and an inorganic substance capable of absorbing a pigment in the ink The method of applying the fine particles to the surface of the base material together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone. The material of the inorganic fine particles capable of absorbing the pigment in the ink may, for example, be a porous oxidized oxide oxidized sol or a special ceramic. Such a sheet for information transfer having an ink receiving layer is generally called an ink jet-dedicated paper, an ink jet-dedicated film, a glossy paper, a glossy film, or the like. An example of a representative commercial product of the sheet for information transfer having an ink receiving layer is, for example, a product name of C_n (share): professional photo paper (pr〇fessi〇nal Photo Paper), and Canon photo paper gloss pr 〇[Platinum grade] and glossy Gold,· Seiko Epson (shares) product name: photo paper 32 201235418

CrisPia (high gloss), photo paper (gloss); 曰本HP (share) product name: Advanced Photo Paper (gloss); FUJI FILM (share) system name: enamel photo finishing Pro; Brother Industrial Co., Ltd. product name: photo glossy paper BP7丨G and so on. Further, the term "plain paper" means a paper in which an ink receiving layer is not provided, and a large amount of various plain papers are commercially available depending on the use. In the commercially available plain paper, for example, two-faced plain paper (made by Seiko Epson Co., Ltd.); PB PAPER GF_5〇〇 (made by Can〇n Co., Ltd.); Multipurpose Paper, All_in-one PHnting Paper (Hp company) and so on. Further, the paper which is not particularly limited to the use of ordinary photocopying paper (Plain Paper C〇Py' PPC) for performing ink jet recording is also plain paper. The coloring system of the present invention means a substance colored by any one of (a) a water-soluble azo compound of the present invention; (b) an ink composition of the present invention containing the chemical substance. And (4) an ink composition of the present invention containing the compound and a water-soluble organic solvent. The material to be colored is not particularly limited, and examples thereof include the above-mentioned materials to be recorded, but $ is limited thereto. Preferably, for example, the above-mentioned material to be recorded 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 and dyeing method, and a screen printing method. The ink jet recording method of the present invention or the like is preferably the ink jet recording method of the present invention. 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 which is not represented by the formula (1) is excellent in solubility in water and a soluble organic solvent. The water-soluble azo compound 俜1 aquatic coupler of the present invention has the following characteristics: In the process of the ink composition of the invention 33, 2012, 354, the filterability to, for example, the membrane filter is good. The ink composition of the present invention is capable of obtaining a yellow recorded image on a material to be recorded, such as plain paper and a sheet for information transfer having an ink receiving layer, the yellow recorded image being very sharp and The chroma and print density are high, and the ideal hue. Therefore, it is also possible to faithfully reproduce the color map of the color tone of the photo on the paper. Further, the ink composition of the present invention does not cause solid precipitation, physical property change, hue change, etc. after storage for a long period of time, and the storage stability is extremely excellent. When the ink composition of the present invention is used as the ink jet ink, the ink composition in the vicinity of the nozzle is not easily precipitated by drying, and the ejector (recording head) is not clogged. Further, the ink composition of the present invention may produce a change in the material (four) # in the following cases: using a continuous ink jet printer to recirculate the ink at a longer time interval; or by requiring An on-demand inkjet printer is used intermittently. Further, the image obtained by recording the sheet for information transmission having the ink receiving layer by the ink composition of the present invention has various properties such as water resistance, thirst resistance, ozone resistance, rub resistance, and light resistance. The solidity is good, and in particular, the ozone gas resistance is good. For this reason, the image of the phototone has excellent long-term storage stability. Further, compared with the conventional ink, the color rendering property such as the upper paper, the brightness, and the printing density of the plain paper is also excellent, and particularly excellent in terms of high chroma. The water-soluble azo compound of the present invention represented by the above formula (1), the water-soluble azo compound of the present invention, is very useful for use in various inks for various recording ink applications. For the recording of ink recordings, the invention is described in the following. Further, unless otherwise specified, "parts" and "%" are the mass basis and the reaction temperature is the internal temperature. In the compound to be synthesized, 'measured by ληιαχ (maximum absorption wavelength) is obtained: a measured value in an aqueous solution of 8. Further, in each structural formula of the chemical substance to be used in the examples, acidic functional groups such as '(iv) and a repeating group are described in the form of a free acid. Further, the compound of the present invention obtained in the examples had a solubility in water of 丨〇〇g/L or more at room temperature. [Example 1] (Step 1) While dissolving sodium hydroxide to pH 6, while dissolving 20.7 parts of 5-amino-2-benzenesulfonic acid in 200 parts of water, 7 parts of sodium nitrite was added thereto. This solution was added dropwise to 2 parts of 5% hydrochloric acid at 0 to 10 ° C for 30 minutes, and then 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, while adjusting the pH to 7 with sodium hydroxide, 23 parts of 2 (sulfopropoxy)aniline was dissolved in 13 parts of water, and 1 part of 4 parts of sodium hydrogen sulfite and 8.6 parts were used. 35% of formalin is produced into a methyl-ω-sulfonic acid derivative by a conventional method. The obtained thiol-omega-sulfonic acid derivative was added to the previously prepared diazo reaction solution, and scrambled at 〇~151:, pH 2 to 4 for 24 hours. After the reaction solution was adjusted to pH 11 with sodium hydroxide, the mixture was stirred at 80 to 95 ° C for 5 hours while maintaining the pH 11 surface, and further added to the gasification surface 35 201235418, which was precipitated by salting out and separated by filtration. A solid was used to obtain 100 parts of the wet cake of the azo compound of the following formula (7). Ho3s(ch2)3o

H2 (9) (Step 2)

Add 250 parts of ice water to the product name LEOCOLRTM TD90 (surfactant) Q ι (), and stir vigorously, add 3.6 parts of trimeric gasification cyanide, and stir it in 〇~5. After a minute, a suspension was obtained. Then, 100 parts of the wet cake of the compound represented by the above formula (9) was dissolved in water 200 and the suspension was added dropwise to the solution over a period of 30 minutes. After the completion of the dropwise addition, the mixture was stirred at ΡΗ 6 to 8, and Μ 45 ° C for 6 hours. To the resulting solution, 22.5 parts of glycine was added, and the mixture was stirred at pH 7 to 9, 75 to 90 °C for 4 hours. After the resulting reaction solution was cooled to 20 to 25 tons, 800 parts of acetamidine was added to the reaction mixture, and the mixture was stirred for 2 hours. The precipitated solid was separated by filtration, whereby 50.0 parts of a wet cake was obtained. The wet cake is dried using a hot air dryer of 80T: whereby the present invention represented by the following formula (10) is obtained.

The sodium salt of the water-soluble azo compound Qmax: 393 〇 nm) 13 5 parts. H03S(CH2)3〇 0(CH2)3S03H

\:H2""C02H

[Example 2] The same procedure as in Example i was carried out except that 18.3 parts of 2-aminoethanol was used instead of 22.5 parts of glycine in Example 丨 (Step 2) 36 201235418, and the following formula (11) was obtained. The sodium salt of the water-soluble azo compound of the present invention shown is 14.0 parts Ainax : 387.5 nm) H03S(CH2)30

H03S ΝγΝ HN 9(ch2)3so3h

So3h (11)

(CH2)2—〇H

[Example 3] The same procedure as in Example 丨 was carried out except that 44.1 parts of glutamic acid was used instead of 22.5 parts of glycine in Example (Step 2), and the present formula (12) was obtained. 72 parts of the sodium salt of the water-soluble azo compound of the invention (ληιβχ: 397.5 nm) 〇

This was carried out in the same manner as in Example i except that 4-aminomethylbenzoic acid was used instead of 22.5 parts of glycine in Example (Step 2), and the following formula (13) was obtained. The sodium salt of the water-soluble azo compound of the invention was 14.5 parts (Imax: 393.0 nm). 37 (13) 201235418

H03S(CH2)39 0(CH2)3S〇3H H· H N=N

WS〇3HΗΪ _ CH2^~^-S〇3H [Example 5] Except that 69.3 parts of (4-sulfophenyl)glycine was used instead of 22.5 parts of glycine in Example 1 (Step 2), The same procedure as in Example 1 was carried out to obtain 14.5 parts (Xmax: 391.0 nm) of the sodium c h3os salt of the water-soluble azo compound of the present invention represented by the following formula (14). H03S(CH2)30

, CH~Q-S03H (14) ) 3h [Example 6] In addition to the use of 2 - (According to the negative, beautiful, Xiaosong. J rolling storm) This amine is 24. 5 parts, instead of implementing you 1 (Step 1) 231 parts of (2-thylpropoxy)aniline, and 56 parts of heart aminophenic acid were used instead of the examples! (I) in the same manner as in Example i except for the glycine I in (Step 2), the water-soluble azo compound of the present invention which is not represented by the following formula (15) is 392.5 nm), and the halon is 14.5 parts amax. .

H〇3S(CH2)4〇 〇(CH2)4s〇3h

HN ___ ^H2~〇~S〇3h 38 (15) 201235418 [Example 7~ι: η (Α) Ink was prepared using the above-mentioned examples 丨~6 compound [sodium salt of formula (10) to formula (10)] In the present invention, the azo nitride VJ .3 . . . and the pigment are mixed and formed into a solution as shown in the following Table 7, and the ink of the present invention is obtained in error. The test ink is prepared by using the obtained 0.45 μm membrane filter to remove inclusions, and the test ink is prepared. Further, the ink for the test is in the range of 8.〇 to 9.5. In the following Table 7, the "surfactant" is a trade name of Surfyn® 1RTM 1CMPG50 manufactured by Shinsei Chemicals Co., Ltd. The preparation of each of the inks using the compounds obtained in Examples 1 to 6 was carried out as Examples 7 to 12, respectively. 39 201235418 [Table 7] 1—^- 1 _ : ~~---- The compound obtained in each example glycerin-3.5 parts I·II.. - part urea s5-.〇份Ν-methyl-2- . Bilo spray | -s_ί.ο 3 0 Isopropanol butyl carbitol 2 0 check interface active agent 0 1 price __ ion exchange water 77 4 pine total - ίοο.ο [Comparative Example 1] In addition to use The compound of the following formula (16); + & human compound was used in place of the compound of the present invention obtained in each example, and the ink for comparison was prepared in the same manner as in the examples 7 to 12. Hydrophobic preparation of this ink is used as a comparative example. The compound used in Comparative Example i is disclosed in 曰本特日日刀. This compound can be used for inkjet ink.

In the publication of the Japanese Patent Laid-Open No. 25-2U No. 22, No. 22 (16), in addition to the use of the dopa- sin described in Example 1 of Patent Document 2, The inks for comparison were prepared in the same manner as in Examples 7 to 12 except for the obtained compounds of the present invention. This ink was prepared as Comparative Example 2.屮鲂You 丨ο & is shown in the following formula (17).

;o3h The structural formula of the compound used in Comparative Example 2 is as follows: (17) In addition to the dye described in the compound No. 14 in the compound example of Table i of Patent Document 2, in place of the compound of the present invention obtained in each Example 5 The rest is carried out in the same manner as the implementation of your "~12, and the ink for modulation comparison is used as the comparative example 3 with the modulation of the ink. The structural formula of the compound used in Comparative Example 3 is represented by the following formula (18).

HN S

H03S(CH2)30 0(CH2)3S03H H〇3s μ-flying 3h (18), (ch2)2—so3h (B) Inkjet recording using inkjet printer (manufactured by Canon Co., Ltd., mus_ip45GG The inks of the above-mentioned Examples 7 to 12 and the respective comparative examples were subjected to ink jet recording on five types of glossy paper (inkjet paper) as a light resistance test, an ozone gas resistance test, and a yellow print. Concentration 卬 test, chroma (c*) test. In the case of performing inkjet recording, an image pattern is produced by y value) using the gradation (darkness level) of the number of steps 2012 201218 to obtain the reflection density, and a recorded matter having a yellow level is obtained. The obtained recorded matter was used as a test piece, and various tests were carried out. Glossy Paper 1 : Canon Co., Ltd. Product Name · Gloss p (7) [Platinum Grade] (PT-101) Glossy Paper 2 : Canon Co., Ltd. Trade Name: Gloss Gold (GL-lOl) Glossy Paper 3 : Seiko Epson Limited Share Company name: Photo paper Crispia (high gloss) Glossy paper 4: HP company name: Advanced photo paper (q886ia) Glossy paper 5: Brother Co., Ltd. Product name: Photo paper (BP71GA4) Photosynthetic test and The ozone gas resistance test is carried out by measuring the reflection concentration of the portion of the recorded matter having the reflection density D closest to the test. The chroma (C*) and the reflection density (Dy value) are the positions where the gradation is the highest. Determination of chroma and reflection density, using a color measurement system (trade name)

Spectr〇Eye_, made by X_rite). The colorimetric system is carried out under the following conditions: The concentration reference is DIN (DeUtsche Indimrie N〇mung c〇w

System), viewing angle 2°, light source D65. The following describes various test methods for recording images and evaluation methods for test results. (C) Xenon arc lamp light resistance test. Each test piece is placed on a support' and a xenon arc lamp weathering test machine XL75 is used. The company system was irradiated for 168 hours at an illuminance of 0.36 w/m 2 at a temperature (10) and a humidity (10) 42 201235418 RH. The reflection density of each test piece after the test was measured by the above color measurement system, and calculated by (reflection concentration after test/reflection concentration before test) X 100 (%), and the residual ratio of the dye was determined. After the results, Examples 7 to 12 and Comparative Examples 1 to 3 all showed good results. (D) Ozone gas resistance test Using an ozone weathering tester OMS-H [manufactured by Suga Test Machine Co., Ltd.], it was allowed to stand in an environment having an ozone concentration of 10 ppm, a humidity of 60% RH, and a temperature of 24 ° C for 24 hours. The reflection density of each test piece after the test was measured by the above color measurement system, and calculated by (reflection concentration after test/reflection concentration before test) X 100 (%), and the residual ratio of the dye was determined. After the results, Examples 7 to 12 and Comparative Examples 1 to 3 all showed good results. (E) Print density test The yellow print density (Dy value) was measured by the above colorimetric system in the gradient portion having the highest reflection concentration in each test piece. The results are shown in Table 8 below. 43 201235418 [Table 8]

Dy value glossy paper 1 glossy paper 2 glossy paper 3 _^_^ paper 4 glossy paper 5 Example 7 1.98 2.07 2.16 1.97 2 16 Example 8 2.06 2.13 2.24 ____2_, 〇2 2.19 Example 9 1.90 2.02 2.12 1.93 2 08 ! Example 10 2.02 2.06 2.13 1.96 2.12 Example 11 1.89 2.03 2.10 2.17 Example 12 2.00 2.07 2.16 ____K97 2.09 1.94 2.01 2.07 1.97 2 ' . 1.85 1.89 1.96 _J.8l 1.93 1.77 . 1.88 1.97 .~ 1.94 The results of Table 8 show that 'in the In terms of the yellow print density (Dy value), both the glossy paper and Comparative Example 2 and Comparative Example 3 showed worse results than Examples 7 to 12. (F) Saturation test The yellow chroma C value was measured by the above U color system for the gradation portion having the highest reflection concentration in each test piece. The results are shown in Table 9 below. 2012 201235418 [Table 9] Chroma ~---- Glossy paper 1 Example 7 110 Example 8 117 Example 9 ----, 108 Example 10 Example 11 107 Implementation Example 12 113 Comparative Example 1 106 Comparative Example 2 --~ 1〇2 Comparative Example 3 1〇4 -------

From the results of Table 9, it can be 'in terms of chroma (C* value), in any glossy paper, Comparative Example 2 is shown to be extremely poor results in 4 Zeze „ α L Soft Examples 7 to 12, and 5 Comparative Examples The 1 and 3 s sentences show a worse result than the examples 7 to 12. 0 From the results of Table 9 and Table 9, it is known that Comparative Example 1 shows the following results: In the yellow printing density (Dy value), in gloss Papers 1 and 2 were good, but glossy papers 3, 4, and 5 were more undesirable than the examples, and in terms of chroma (C* value), any gloss paper was worse than the examples. In Comparative Example 2, the following results were obtained: in terms of the yellow printing density (Dy value), it was poor in any glossy paper, and in terms of chroma value, any glossy paper was more inferior than the respective examples. Example 3 shows the following results: in terms of yellow print density (Dy value) and 45 201235418 chroma (c value), any gloss paper is more disadvantageous than the respective examples. Result: in all the light in terms of chroma (C* value) and yellow print density (Dy value) of the recorded matter It is understood that the water-soluble azo compound of the present invention and the ink composition of the present invention containing the compound have a high-definition hue and yellow in various glossy papers as compared with the conventional dye. The printing density value is high, and the color rendering property is excellent regardless of the type of the glossy paper. [Industrial Applicability] The water-soluble azo compound of the present invention of the yellow pigment, and the water-soluble azo compound The yellow ink composition of the present invention can obtain a recorded image with high color development and scent. Therefore, the compound and the ink composition containing the compound are very useful for various recording purposes, and particularly for ink jetting. Recording purpose [Simplified description of the diagram] No [Main component symbol description] None 46

Claims (1)

201235418 VII. Patent application scope: • A water-soluble azo compound or a salt thereof, which is represented by the following formula (1): 〇(CH2)xS |^〇ΗΜ=Ν H03S(CH2) X0 0 (CH 焱SO3H 〇3Η (1) H〇3 Plant N^N (wherein 5 X represents an integer of 2 to 4, and the base is an amine group represented by any one of the following formulas (2) to (6)) V , (CH2 y-C02H In the formula (2), y represents the integer of Bu 5) (2) / NN(CH2)w-〇H (in the formula (3), w represents an integer of 2 to 6) (3) ^ Nv-COzH (CH2)mC02H (in the formula (4), m represents 1 or 2) (4) -NH „ (5) (In the formula (5), η represents an integer of 0 to 2, a sulfo group) Hydrogen source co2h or R (in the formula (6), R represents a hydrogen atom or a contig). The water-soluble azo compound according to the first aspect of the invention is the salt of the formula (1), wherein the enthalpy is 3. 3. The water-soluble azo compound of the above formula (1) or a salt thereof, wherein the water-soluble azo compound represented by the above formula (1) is as shown in the following (7): Fly H03S (CH2) ) 30 ho3s 9(ch2)3so3h HN. N=N> 〇-CI (7) so3h - C02H 4. The ink composition of the invention, which contains the water-soluble azo compound or a salt thereof according to any one of the above-mentioned claims . 5. The ink composition according to claim 4, which contains a water-soluble organic solvent. 6. The ink composition of claim 4, which is for recording. ^ 7. An inkjet recording method which uses an ink composition as described in the scope of the patent application as an ink, and causes ink droplets of the ink to be ejected on a recording material according to a recording signal to be recorded. . 48 201235418 wherein, the film of the layer is the inkjet recording method described in the seventh aspect of the patent application. The material to be recorded is a sheet for information transmission. The inkjet recording method according to Item 8, wherein the information transfer sheet is plain paper or has an ink receiving material, and the ink receiving layer contains a porous white inorganic material. 10. A coloring body which is colored by any one of the following: (4) a water-soluble azo compound or a salt thereof as described in the scope of the patent application, (9) containing the item i of the patent application scope An ink composition of the water-soluble azo compound or a salt thereof; and an ink composition containing the water-soluble azo compound or a salt thereof and a water-soluble organic solvent as described in the scope of the invention. - A coloring body which is colored by an ink jet recording method as described in claim 7 of the patent application. An ink jet printer which is filled with a container containing the ink composition as described in claim 4 of the Japanese patent application. 49 201235418 -N: (3) (ch2)w-〇h ~HN-pC02H (4) (CH2)mC02H -NH -VH2)n-^z (5) co2h Η 1 /=\ N CH---- ---^ (6) III. Abstracts of English Invention: None. The designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 2