TW201233732A - 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, excellent 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 formula (2) or formula (3). In formula (3), R represents a hydrogen atom or a sulfo group.

Description

201233732 VI. Description of the Invention: [Technical Field] The present invention relates to a water-soluble bis-azo compound or a salt thereof, a composition containing the ink, and a color body obtained by coloring the same . [Prior Art] Among various color recording methods, various ink ejection methods have been developed as one of the representative methods by the ink jet printer. These are all caused by the generation of ink droplets (ink droplets), and the ink droplets are attached to various recorded materials (paper, paper, cloth, etc.) for recording.盥妯〃The material that is recorded by z is not in direct contact, so it is less quiet and quieter. In addition, this method has the characteristics of being easy to be miniaturized, high-speed, and colorful, and has been characterized by recent years. It is rapidly spreading, and it is expected to grow substantially in the future. In the past, pens or signatures, inks for inks, and inks for inkjet recording, - inks used directly, which are water-soluble pigments. (dye) is dissolved in an aqueous medium. In these aqueous inks, a water-soluble organic solvent is generally added to prevent the ink from being clogged at the tip of the pen or the ink ejection nozzle. The following properties are required for such inks: Recording image with sufficient concentration, no: clogging of the pen tip or nozzle, good drying property on the material to be recorded, less turbidity, excellent storage stability, etc. In the case where the nozzle is near the nozzle, the water in the ink of 201233732 evaporates faster than other solvents or additives, and forms a state in which the water is less and the solvent or the additive is more. At this time, the pigment will solidify and precipitate. One of the important required properties is that even if it is formed in a state where the amount of moisture in the ink is small, the solid is not easily precipitated. Therefore, the reason ',, the solubility in a solvent or an additive is high' is also a property required for the dye - In addition, 'the method of solving the nozzle clogging' is known to use a method of printing a pigment having a higher concentration. By using a pigment having a higher printing density, _ can maintain the conventional printing density and reduce the pigment content in the ink. This situation does not 'only make the pigment not easy to precipitate, and it is also advantageous on the cost side, and it is desirable to develop a pigment' which has a higher printing density. However, 'by inkjet printer, color When recording images or text information on a computer's color display, it is generally a subtractive color blend that uses yellow (7), magenta (M), and cyan (ah) ( ~ 4 colors of black (K) ink are used to display the recorded image in color. In order to reduce the color of the mixed image, the CRT (Brown Tube) display and the like are made of red (R) and green as much as possible. (6) The additive color image obtained by the blue color (8) is faithfully reproduced, and it is desirable that each of the pigments used in the ink, among them, Y, M, and C' respectively have a hue close to the standard color and is sharp. The sharpness 'generally means that it has a high chroma. When using the three primary colors of Y, M, and C with low chroma, the color gamut that can be expressed in a single color or a mixed color will be narrowed, and the range of the color gamut to be revealed may be Therefore, it is desired to develop a high-color pigment and an ink containing the pigment. In addition, the performance of the ink is required to be stable for a long period of time, and the density of the recorded image is high, and the image is high. Water resistance, moisture resistance, light resistance, and 201233732 Excellent gas resistance. Here, the term "gas" refers to resistance to a phenomenon in which an oxidizing gas (also referred to as an emulsifiable gas) existing in air is recorded on an image to be recorded or recorded. The pigment (dye) reacts to change/fade the recorded image. It is generally considered that the 'oxidizing gas, particularly ozone gas' is the main cause of the change/fading phenomenon of the ink-jet recorded image. This change/fading phenomenon is a peculiar phenomenon for inkjet recording of images, so that it is an important technical problem in the field to improve the ozone gas. Due to the development of inkjet technology in recent years, the speed of inkjet recording (printing) is significantly improved. This is the same as the laser printer using electronic toner (t_r). The printing of documents on plain papers tends to use inkjet printers. The inkjet printer has the following advantages: the type of recording paper is not selected, and the printer itself is cheaper, especially in Soho (Curry: Small Office H0me)

The Office) family, etc., 丨, ~ λ in the 1 office environment is gradually popularized. When using an inkjet printer in such a use for printing, there is a way to pay more attention to hue, color (printing) density, and pigment ink in the printing == quality. In the ink, it is not cut: the second 'pigment ink is not dissolved in water, so if the 嗲mk liquid state' is the ink in the dispersed state, the right is used for the problem of inkjet stability and Ji Feifei A is a problem of resistance to clogging when the pigment ink for the ink itself is used. In addition, when it is considered to be less easy: & When dye ink is used, it is easy to cause the above problems, but especially in the water resistance 201233732, it is obviously thicker than the water, and the water is more bad. Therefore, it is strongly expected that the dye is different from the pigment ink. The pigment on the surface of the back surface m 3 of the ink jet is more quickly smeared toward the paper > ^ °, and as a result, the problem of a decrease in the color development density is likely to occur. One of the methods of inkjet image recording of a photo-quality image is a method in which the ink-receiving layer is placed under the name of the material to be recorded. For such an ink-receiving layer, a porous white inorganic substance is often contained to add dryness and reduce pigmentation under high image quality. However, especially in the _ material of ::, it is possible to significantly observe the above-mentioned ozone gas = / secret color. Since the recent digital cameras and color printers have been printed by digital cameras in the form of photo quality, the opportunities have increased. Therefore, the above-mentioned recording fading caused by oxidizing gases has become a problem. Compared with the magenta and other ratios of the other three primary colors, regarding the yellow pigment, pigments having light resistance to resistance to oxidizing gases have been proposed so far. However, it has not been possible to obtain a yellow pigment and a yellow ink, which are sufficient to satisfy the high vividness and various firmness required by π. A conventional yellow pigment for inkjet which is excellent in water solubility and sharpness = such as · aL (C ° 1 C) r Index ''color index) Direct Yellow 132. In this plural, yellow pigments for inkjet recording have been developed, and therefore, a plurality of azo dyes which are still solid in cattle have been proposed. Patent literature! It is revealed that a yellow water-soluble property has high solubility in water, and has endurance and light resistance. Patent Document 2 discloses a yellow water-soluble azo compound which is highly soluble in water and has moisture resistance, ozone gas resistance, and light resistance. Patent Document 3 discloses a yellow water-soluble azo compound which is soluble in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance. Patent Document 4 discloses a yellow water-soluble azo compound which has high solubility in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance. [Prior Art Document] (Patent Document) Patent Document 1: U.S. Patent No. 6,867,286, Patent Document 2: JP-A-2006-152244, Patent Document 3: International Publication No. 2008/053776 Patent Document 4: JP-A-2009 SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a water-soluble yellow pigment (a character) and a yellow ink composition containing the yellow pigment, which is It has high solubility, and has high color rendering property (printing density) of recorded images, and is excellent in chroma. The yellow ink composition is used for various recordings, particularly inkjet inks. [Means for Solving the Problems] After the inventors of the present invention made efforts to solve the above problems, it was found in 201233732 that a water-soluble azo compound represented by the following formula (1) has the water-soluble solution. Sexuality _ Children The ink composition of the 3 nitro compounds can solve the above problems, and the present invention has been completed. In other words, the invention relates to the following. 1)

A water-soluble azo compound or a salt thereof, which is represented by the following formula (1): H〇3S(CH2)x〇 0(CH2)xS03H

(wherein X represents an integer of 2 to 4, and the base A represents an amine group represented by the following formula (2) or (3)) (2) (3) /CH2—C02H CH2—co2h ch2_^

And a salt of the water-soluble azo compound according to the above 1), wherein X is 3 in the above formula (1), wherein R is a hydrogen atom or a sulfo group. . (3) The water-soluble azo compound according to the above formula (1), wherein the water-soluble azo compound represented by the above formula (1) is represented by the following formula (4):

'S 201233732 ho3s(ch2)3o 9(ch2)3so3h

4) An ink composition containing the water-soluble azo compound according to any one of the above 1) to 3) or a salt thereof. 5) The ink composition according to the above 4), wherein the further contains a water-soluble organic solvent. 6) The ink composition according to the above 4), which is used for inkjet recording. 7) An ink jet recording method using the ink composition according to the above 4) as an ink, and causing the ink droplets of the ink to be ejected on the recording material in accordance with the recording signal to be recorded. The inkjet recording method according to the above 7), wherein the recorded material is a sheet for information transmission. The ink jet recording method according to the above 8), wherein the information transfer sheet is plain paper or a sheet having an ink receiving layer containing a porous white inorganic material. 201233732 ίο) The coloring body' is colored by any one of the following: (a) a water-soluble azo compound as described in 1) above or a salt thereof; (b) containing the above 1) An ink composition of a water-soluble azo compound or a salt thereof; and (C) an ink composition containing the water-soluble azo compound as described above or a salt thereof and a water-soluble organic solvent. 11) A color body It is colored by the inkjet recording method according to the above 7). 12) An inkjet printer is filled with a container containing the ink composition as described in 4) above. 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 ink composition of the present invention containing the medium or a salt thereof In the course of the object, for example, the membrane thief has good filterability, and the image obtained by using the conventional compound is recorded by the ink composition of the present invention having the compound of the present invention. The image 'printing density and chroma are more excellent. In this case, the above formula (1) is shown. The water-soluble azo compound of the present invention or a salt thereof, and an ink composition containing the water-soluble azo compound or a salt thereof are very useful for various recording applications, and are particularly useful for the purpose of recording inks. 10 201233732 [Embodiment] The present invention will be described in detail below. The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof is a water-soluble yellow coloring matter. Unless otherwise specified, an acidic functional group such as a sulfo group or a carboxyl group is represented by a free acid form. Further, as described above, the present invention contains the above formula (1) = a azo compound And the salt of the compound, but it is often the same at the same time. It is too complicated to carry the "compound or its salt". Therefore, unless otherwise specified, the "inventive, convenient, or re-stepping, hydrated (azo) compound azo) compound is included. The invention is of the invention (water-soluble, the compound of the invention is as described above)

The integer of the table... is better. (1) In the above formula (1), 'X = 'base cut in the formula (1)) or an amine group of _*. good. The above formula (3) towel, the group base, and the (iv) group are preferably the group A, and the amine group represented by the above formula (2) is preferred. Among the above-mentioned bases 8, feet and x, the combination is better, and the combination of the two components is more similar. Better. Preferred and Preferred Groups The compounds of the above formula (1)-mt(4)* are particularly preferred. The compound of the present invention can be produced, for example, in accordance with the following 11 201233732. Further, the groups A, R and X which are suitably used in the following formulae (AA) to (G) respectively have the same meanings as those of the base A, the ruler and the oxime in the above formula (1). A compound represented by the following formula (ΑΑ) is obtained by using a commercially available 2-aminophenol as a raw material and a compound represented by the following formula (ΑΑ) is obtained by a conventional method, and a compound represented by the following formula (ΑΑ) is used using sodium hydrogensulfite and formalin. Conversion to a methyl _ω-sulfonic acid derivative represented by the following formula (Β), and then 5-amino-2-chlorobenzenesulfonic acid represented by the following formula (c) is carried out by a conventional method. After diazotization, at a reaction temperature of -15 ° C, pH 2 to 4, it is coupled with a methyl-ω sulfonic acid derivative represented by the following formula (B), and then at a reaction temperature. 8〇~95(>c, pH 10.5 to 11.5, a hydrolysis reaction is carried out, thereby obtaining a chemical & the substance represented by the following formula (D). Further, the method of the present synthesis is based on JP-A-2006-152244 The method described in the tenth bulletin is carried out.

0(CH2)xS03H 0(CH2)xS03H

2 〇-nh2 (\^so^ (B) (ΑΑ) H03S(CH2)x0

H2 Then, at a reaction temperature of 15 to 45 t 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 trimeric gasified cyanide (1 equivalent) are used. Condensation, whereby a compound represented by the following formula is obtained. 12 201233732

〇(CH2)xso3H Η ΗVV ΝγΝ Cl(Ε)

Clso3H is further substituted by the above-mentioned formula (E) with an amine represented by the formula (F) or (G) at a reaction temperature of 75 to 9 〇t: 'pH 7 to 9 The chlorine atom on the triazine ring in the compound, i.e., the compound of the present invention represented by the formula (1), and the CH2-CO2H represented by the formula (1) can be obtained. ,ch2—co2h (F)

R, R H- (G) 'ch2—the amine represented by the formula (F) can easily obtain the amine of the imidodiacetic acid and the amine represented by the f(G) For example, diphenylcarbamate or [(4-sulfophenyl)methyl]amine can be mentioned. In Table 1, the specific examples of the compound of the present invention which are not in the formula (1) are as follows: However, the present invention is not limited to these specific examples. Furthermore, in Table 1 below, a certain ^ and X. The compound bat~ corresponds to the above formula (1) or the base A of R 唬 1 to 3 in the oxime is the above-mentioned formula (specific examples of the compound, and a specific example of the compound in which the compound is present in the amine group) is "the above formula (7) Institute - 13 201233732 [Table i]

Compound braided structural formula XR 1 2 H03S(CH2)2〇c Ch-0-Ν^-^-Νγ^Ν-^ ho3s ΝγΝ H02C-H〆\h2- )(ch2)2so3h 3-n=nQ-ci So3h -co2h 2 3 ho3s(ch2)3( Ch-〇*N=N"^ ho3s ho2c ) ( 3(CH2)3S03H 3-n=nQ-ci so3h -co2h 3 4 ho3s(ch2)4o c H03s ΝγΝ ho2c -h2Ah2- 〕(ch2)4so3h 3-n=n-〇-ci so3h -co2h 4 3 Η H03S(CH2)30 0(CH2)3S03H Ch-Q^=N-^N^NYN-0-N=NQ -CI H03S ΝγΝ S03H 5 3 S03H ho3s(ch2)3c ci-〇-n=n-^ ho3s h〇3s-〇- ) c -H2〆\η2· )(CH2)3S03H 3~n=nQ-ci so3h O~S03H 14 201233732 The compound ' represented by the formula (1) is also present in the form of a free acid or a salt thereof. The compound represented by the above formula (1) may, for example, be a salt with an inorganic cation sub-organic % ion. Inorganic cations Alkali gold; | @^ 4 The dish /, the system can be, for example, genus: for example: salt, sodium salt 'potassium salt and other salts; and Lai Lan 4+). In particular, the salt of the organic cation is, for example, a salt of the fourth grade shown by the following formula (5), but is not limited thereto. D (5) Z X Z2 In the upper 3 (5), ~ each independently represents a gas atom. ~C4 ~. 4, a base, or a base of ~4 alkoxy ci~c4 ... Z~Z4 at least "solids a base other than a hydrogen atom. Here, Z 1 ~ Z4 Φ 夕μ, +,, towel 1~C4 burn Examples of the base include, for example, ruthenium. Similarly, examples of the above-mentioned 1 to C4 alkyl group include, for example, a thiol, a platinum ruthenium earth, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and the like. λ, butadiene, 3'-butyl, 2,hydroxybutyl, etc. Similarly, examples of the above-mentioned hydroxy:~C4 alkoxy C1 to C4 alkyl group include, for example, ethoxycarbonyl 2 ethoxy group. Ethyl, 3-(hydroxyethoxy)propyl, 3-(hydroxy), butyl, 2-(hydroxyethoxy)butyl, etc. Among the above salts, preferred are, for example, sodium salts and potassium salts. = salt; #ethanolamine salt, diethanolamine salt, triethanolamine salt, early isopropanolamine oxime, _g dish, isopropanol salt, triisopropanolamine salt, etc. ' Recording salt, etc.. In this case, it is preferred to use a salt of a bell, a salt of a salt and a salt of a salt. Knowing that the salt or free acid of a compound of the formula (1) which is well known to those skilled in the art, Can be used by the following 15 201233732 :: It is easy to obtain. A solid which can be obtained by filtering the compound represented by the above formula (1) can be precipitated by, for example, the above-mentioned cutting step = 'the final step in the synthesis reaction of the solid In the aqueous solution or the like of the salt of the compound of the compound represented by the compound (1), a method of adding a water-soluble organic solvent such as an alcohol: a method of adding a gasification organic solvent, etc. After the obtained sodium salt is thirsty - after adding _ 酴笙 Α Α 丄 虑 虑 虑 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛 洛a mixture of the free acid and the salt of the compound. One of the compounds is a free acid and a sodium salt of the steel salt, a wet cake which can be obtained by using the obtained sodium salt or a dry solid thereof <& Adding chlorine (tetra), etc., and adding an acid such as hydrochloric acid to adjust the hydrazine to, for example, pH1 to 3, and then separating and separating the precipitated solids to obtain the compound represented by the above formula (1) (4). The amount of gasification recorded or/and the rush, The following mixture can be obtained: a mixture of the salt and the sodium salt of the compound represented by the above formula (1); a mixture of the free acid and the ammonium salt of the compound represented by the above formula (1), and the like. In the reaction mixture after the reaction, a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) is added to directly obtain a solid of the free acid. At this time, the free acid cake of the free acid of the compound represented by the above formula (1) is added to water and stirred. Thereafter, the following compounds are added to produce a salt, and it is also possible to obtain a potassium salt, a clock salt, a salt, a quaternary salt, etc. corresponding to the compound to be added. The compound is, for example, potassium hydroxide, hydrogen. Oxidation clock, · ammonia 201233732 Κ 'The organic quaternary ammonium hydroxide shown in the formula (5) is a number of swims: the number of moles of k to limit the addition of the above hydroxide;: number, can also be modulated For example: the molar salt of the bell and the salt of the salt, etc.; 2: salt 4; and the salt of the compound of the formula (1), and the salt of the compound of the formula (1); (4)::: the type of the salt varies: Physical Li such as solubility, ink used in ink Performance. It is preferable to select the type of salt because of & The compound of the present invention according to the above formula (1) can be used in the form of a free acid such as a deer-like acid and is isolated as a solid free acid, and an inorganic salt (inorganic salt) in the form of an impurity. The salt of the machine is, for example, a gasified sodium or sodium sulphate, etc. The free acid of the compound according to the invention as described above can be treated by the cake or its dry (four)' in water with the desired inorganic or enthalpy treatment as described above. 'The solution of the salt of the corresponding compound is obtained. For the inorganic test, for example, a metal oxide such as a hydroxide clock, sodium hydroxide or potassium hydroxide, an oxide; an alkali metal carbonate such as lithium carbonate, sodium carbonate or carbonic acid; An example of an organic test, for example, an organic amine corresponding to the fourth-order clock of 7F of the above formula (7), which is, for example, an amine such as diethanolamine or triethanolamine, but The compound of the moon is suitable for dyeing natural and synthetic fiber materials or blends and is suitable for the production of ink for writing and ink for inkjet recording " as shown in the above formula (1) Synthesis of the compound of the invention The reaction liquid after the end of the last step can also be used as it is to produce the ink composition of the present invention. However, the reaction liquid or the like can be dried by a method such as the above method or spray drying, and After 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) in water or water and a water-soluble organic solvent. A mixed solution (also referred to as an aqueous medium) mixed with water and added with an ink preparation agent as needed. When this ink composition is used as an ink for an inkjet printer. It is preferable to use a content of the following inorganic impurities: a chloride of a metal cation such as sodium hydride; a sulfate such as sodium sulfate, which is contained as an impurity. In this case, relative to the above: (1) The total mass of the compound shown, for example, the total content of sodium chloride and sodium sulfate is about 1% by mass or less, and the lower limit is 〇% by mass, that is, below the detection limit of the detection machine. The method for producing a compound having less inorganic impurities may, for example, be a method which is known per se by a reverse osmosis membrane; a dry product of the compound of the present invention or a wet cake, for example, acetone, heart-to-alcohol (a method of performing suspension purification or crystallization in a water-soluble organic gluten or a water-soluble organic solvent such as a mercapto alcohol, ethanol, or isopropyl alcohol), and the like, and desalting treatment by such a method In the total mass of the ink composition, the ink composition of the present invention contains 01 to 20% by mass of the compound represented by the above formula (1), preferably 1% by mass, preferably 2 to 8% by mass. The ink composition of the present invention is prepared by using water as the medium f, and within the scope of the effect of the present invention, it is appropriate to use an organic solvent and an ink preparation agent as needed. 7吟201233732 Water-soluble organic solvent system It has the following effects: it dissolves the dye. Prevents the composition from drying (protected, s 'wet state); adjusts the viscosity of the composition; the pigment penetrates into the recorded material. Heke, adjusts the composition The surface tension; the product defoaming, etc., and it is preferable to include a water-soluble solvent in the ink composition of the day. Examples of the ink preparation agent include a preservative antifungal agent, a pH adjuster, a cardiac reagent, a rust preventive, an ultraviolet absorber, a viscosity adjuster, and a dye dissolving agent. Conventional additives such as anti-fading agents, surface tension modifiers, and antifoaming agents. The content of the water-soluble organic solvent relative to the total mass of the ink composition of the present invention is preferably from 〇 to 60% by mass, preferably from 1 〇 to 5 〇% by mass, preferably from 〇 to 20% by mass, to 〇~ 15% by mass is preferred. In the ink composition of the present invention, the remainder of the compound represented by the above formula (1), the water-soluble organic/treat agent, and the ink preparation agent 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, and N, N-di Amidoxime such as methyl decylamine, N,N-dimercaptoacetamide, 2_pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, Heterocyclic ketones such as methyl sulphate-2-ketone, 1,3 - methyl hexahydro-bite 2- 2⁄4; acetone, methyl ethyl ketone, 2-methyl-2-hydroxy ketone 4-ketones such as ketones or ketones, such as quaternary oxime, tetrad π 013 ⁄ ⁄ ⁄, dioxane, etc.; ethylene glycol, 1,2·propanediol, hydrazine, 3-propanediol, hydrazine, 2·butyl Alcohol, 1,4-butanediol, 1,6-hexanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethyl alcohol 'polypropylene glycol, sulfur diethanol (thi〇 Diglyc〇l) such as mono-, oligo or polyalkylene glycol or thioethylene glycol having a C2~C6 alkylene group;

S 19 201233732 Polyhydric alcohols such as propylene glycol, glycerol and hexamethylene glycol monof-flycol triol (preferably triols, ethylene glycol monoethyl ether, ethyl methacrylate, diethylene glycol) Methyl hydrazine, tris. alcohol single butyl test (butyl carbitol h triethyl ether; ketamine single alcohol such as alcohol early ether), on top;; dimethyl sub-repair The secret is plus the coffee, etc.. The base is burned in the same way as in the regular: organic solvent, which also contains, for example, solids, which still shows water solubility, =: However, the substance " even if it is used. For the sake of convenience, as long as such a substance is still expected to be used in the same manner as described above, that is, the package 3 is in the range of a water-soluble organic solvent. Preferred as the above-mentioned water-soluble organic solvent is: Isopropanol, glycerol, ethylene glycol, ethylene glycol, triethylene glycol 'dipropylene glycol, 2 _. pyrrolidone, radioyl 2 - 2 ratio ketones, N-methyl -2-吼Luo phase, tri-methylpropane, and butyl carbitol, isopropanol, glycerol, diethylene glycol, 2: specific ketone, N_mercapto-2 "Bilo (four), The butyl carbitol is preferably used alone or in combination. The above-mentioned antiseptic and antifungal agent may, for example, be an organic sulfur system, an organic nitrogen sulfur system, an organic iS system, a (tetra) propyl group, or a dish. Fast propyl, hydrazine, thiol system, benzothiaz〇le, nitrile, pyridine, 8-hydroxyquinoline, isothiazoline, dithiol, pyridine System, nitropropane, organotin, phenol, quaternary ammonium, tri-till, thiadiazine, ani- ane, diamond, diatom, 201233732 Examples of the compound of the f-acid, the (tetra)ketone (b_Gindan), the benzyl acetate, and the inorganic salt. The organic south-based compound may, for example, be sodium pentachlorophenol, and the pyridine oxide-based compound may, for example, 2_ The pyrithione small oxide sodium salt 'isothiazoline-based compound may, for example, be: u-benzisothiazolin-3-one, 2-n-octyl group _ heart-sold 嗤琳_3_嗣, 5_gas_2 _methyl ice different (four) Lin-3-ketone, 5-gas-2_f-based ice-like (tetra) ketone magnesium, 5_ gas_2_subunit _4 · 嗟 嗟 琳 _3_ 鲷 chlorination 2—Methyl Iisoindole.—ketone ruthenium chloride, etc. Other antiseptic and antifungal agents include, for example, sodium acetate, sodium sorbate, sodium benzoate, and the like; and the trade name of the company Chemical Co., Ltd., p y GXL(S) Or ProxelRTM xl_2(S)箄.▲, 彡 再 , , , , , , , , , , , , , , , , , , , , , , , , 上 上 上 上 上 上 上 pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH Further, any pH can be controlled by controlling the pH of the ink to a range of, for example, 60 to η 6.0 6.0 to U. For example, ^ ^ , alkanolamines such as acetaminophen and triethanolamine, hydroxides of hydrazine hydroxide, sodium hydroxide, gas oxidized dike emulsification, etc.; ammonium cerium oxide, lithium carbonate, sodium carbonate , anti-eye owing to alkali metal carbonate such as potassium. Amine sulfonic acid such as taurine. The disodium tetraacetate, the sodium triazoacetate, the sodium diethylenetriamine pentaacetate, and the urinary chelating agent may, for example, be sodium succinate, sodium chloroethylethylenediamine triacetate, sodium pyrimidine diacetate or the like. The anti-iron agent may, for example, be an acidic sulfoxide, a sodium thiosulfate, an ammonium thioglycolate, a diisopropylammonium nitrite, a tetrahydrofuran, a vinegar, a sulphuric acid, and a sulphuric acid. Cyclohexylammonium and the like. Examples of the ultraviolet absorber include, for example, a compound of the present invention, a compound of the formula, a compound of a cinnamic acid compound, and the like. Further, it is also possible to absorb ultraviolet rays such as fluorescent whitening agents represented by the compound. a compound of a π-well system, a compound in which stilbene is fluorinated with I and benzoxazole, that is, a water-soluble cellulose compound, a viscosity-adjusting agent, and a soluble polymer compound other than a water-soluble organic solvent, For example, polyvinyl alcohol, a polyamine, a polyimine, etc. are mentioned. The ε-caprolactam and the carbonic acid ethylene dye dissolving agent may, for example, be urea ester or the like. Among them, it is preferred to use urea. The anti-fading agent is used for the purpose of improving the preservation of the image. Anti-caries agent can be used: various organic and metal mismatched (d) anti-fade agents. The organic anti-fading agent may, for example, be hydrogen (tetra), alkoxy, di-alkoxyphenols, phenols, anilines, amines, dihydroanthracene (in-class, Chr〇mane) Examples of the metal complex include a nickel complex, a zinc complex, etc. The surface tension adjusting agent may, for example, be a surfactant, and may, for example, be an anionic interface activity. a surfactant, an amphoteric surfactant, a cationic surfactant, a nonionic surfactant, etc. The anionic surfactant may, for example, be an alkyl sulfocarboxylate, an alpha olefin sulfonate or a polyoxyethylene alkyl ether acetate ( P〇ly〇xyethylene aikyi ether acetate), N-decylamino acid and its salt, N-mercaptomethyl taurate, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxygen Vinyl alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl sulfate, alkylphenol phosphate, alkyl phosphate, alkyl aryl sulfonate, 22 201233732 diethyl contig Sodium (iv) salt, 2-ethylhexyl-based succinate, dioctyl sulfosuccinate, etc. The ionic surfactant may, for example, be a 2-vinylpyridine derivative or a poly(4-vinylpyridine) derivative, etc. The amphoteric surfactant may, for example, be lauryl dimethylaminoacetic acid betaine or 2-alkane. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Acids, other imidazoline derivatives, etc. Nonionic surfactants may, for example, be polyoxyethylene phenyl phenyl scales, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxygen Ethers such as vinyl oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; polyoxyethylene oleate, polyoxyethylene distearate, & sorbitan laurate, sorbose Alcoholic liver monostearic acid, & sorbitan monooleic acid vinegar, sorbitol needle sesquiol _, polyoxyethylene oleic acid oleic acid, polyoxyethylene stearate and other ester systems; 4,7,9-tetramethyl_5·decyne_4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl small _3 material B fast diol (alcohol) system; The trade name of the company is "Kiss (4) (4) 104, Surfynol (4) 82, Surfyn〇lRTM 465, (10) (6) (4) stg; SIGMA-ALDRICH company's trade name Tergit〇lRTM 15 S 7 etc. Shoulder/package can be, for example, high oxidized oil The compound, the glycerin fatty acid ester compound, the fluorine compound, the oxime compound, etc. These ink preparations can be used singly or in combination. Further, the surface tension of the ink composition of the present invention is usually 25 to 7 〇. mN/m is preferably 25 to 60 mN/m, and the viscosity is adjusted to 30 mPa.s or less, preferably 23 201233732 20 mPa.s or less. 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 preferable to perform precision filtration. The aperture used in the precision calculation (4) is usually dip 1 μπι, preferably 〇.8~0.1. The compound of the invention is invented by you. It is printed, photocopied, marked, written, drawn, printed, or recorded. (In particular, the ink composition of the present invention, in addition, the ink composition of the present invention, even the ink printer The recording head of the recording head is not easy to be solid, and it is not easy for the recording head to clog. For this reason, the inkjet recording method is used to describe the ink composition of the following method. The container of the object is a method in which the device filled with the hairpin is loaded on the inkjet printer, and the ink composition of the present invention is used as a 'recording signal to eject the ink that is in violation of the ink. Drop the a to make it adhere to the material to be recorded, and 隹...3. The ink-printing machine has the following method: and the mechanical vibration of the machine is used: Lie's printer, for example :use

Bubble jet (note the letter of the bubble generated by heating) and so on. Use it in any way. * The inkjet recording method can sometimes be used for the purpose of obtaining a higher-quality image.

24 201233732 Two kinds of inks with the same pigment are loaded in the inkjet printer. The difference between the two types of inks is the content of the pigment, so that one of the inks becomes a higher-content ink, and the other ink becomes a lower-content ink, and is 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. In addition, the compound of the present invention is used in combination with a magenta pigment or a cyan pigment for the purpose of coloring other colors of ink, for example, black ink, or for the purpose of modulating red ink or green ink. Further, in order to obtain the blue recorded image, the ink composition of the present invention and the ink of the following colors can be made: magenta, f blue; and: green, blue (or green) (or Purple), red, black, etc. At this time, / can be used for inkjet recording in such a manner that the inks of the respective colors are actually charged in the respective valleys and the containers are loaded at predetermined positions of the ink jet printer. The material to be recorded used in the ink jet recording method of the present invention may, for example, be: a sheet for information transfer such as "film", a fiber and cloth (cellulose, samurai, sheep, etc.), and a substrate for a color film. Etc. It is better to use the sheet for f-transmission. There is no special restriction on the sheet for § courier. 'Ordinary paper can of course be used. It can also be used as a surface finisher. Specifically, it is provided with a receiving layer on the following substrate. The substrate is: paper, combination, film, etc. The so-called ink 25 201233732 receiving layer refers to a layer having the following effects: sighing water to speed up its selection, etc. The ink receiving layer is as follows The method is to set, ', and extract a person such as: a method of impregnating a cationic conjugate with the above substrate, or applying a cation to the substrate; A method of applying the inorganic fine particles to a surface of the substrate together with a hydrophilic polymer such as polyvinyl alcohol or polyethylene (tetra) (tetra), etc. The material of the inorganic fine particles capable of the pigment in the ink may be, for example, porous.矽 矽 矽, oxidized sol, special Such a tablet for information transmission having an ink receiving layer is generally called an inkjet paper, an inkjet special film, a glossy paper, a glossy film, etc. A sheet for information transmission having an ink receiving layer Examples of representative commercial products include, for example, Canon (trade name) product name: professional photo paper (Pr〇fessional Ph〇t〇paper), c_n photo paper gloss Pro [platinum grade] and gloss G〇ld; Seik 〇Eps〇n (share) system name: photo paper Cnspia (high gloss), photo paper (gloss); 曰本Hp (share) system mouth name · two-level photo paper (Advanced ph〇t〇Paper) ( Glossy printed company FILM (share) system name: 昼 color photo finishing pr〇; Industrial Co., Ltd. product name: photo gloss paper BP7 丨 G, etc. In addition, the so-called plain paper means that no ink is set A layer of paper has been commercially available in a large variety of plain papers. Commercially available plain papers include, for example, two-faced plain paper (made by Seiko Epson Co., Ltd.); pb PAPER GF-500 (canon Co., Ltd.); Multip Urpose Paper, All-in-one Printing Paper (manufactured by HP), etc. In addition, plain paper copy 'PPC paper, etc., which is not particularly limited to inkjet recording, is also plain paper. 26 201233732 本The coloring system of the invention means coloring by any of the following: a substance: (a) a water-soluble azo compound of the invention; (b) an ink composition of the invention containing the chemical substance And (4) an ink composition of the present invention containing the compound and a water-soluble synthetic organic guest agent. The material to be colored is not particularly limited, and examples thereof include, but are not limited to, the above-mentioned materials to be recorded. 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 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 printing method of the present invention is preferred. The water-soluble azo compound of the present invention represented by the above formula (1) is excellent in solubility in an aqueous water-soluble organic solvent. Further, the water-soluble niobium compound of the present invention is characterized in that it is excellent in, for example, a membrane crucible in the preparation process. The 榀 榀 丄 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋And the chroma and printing are highly affected, which is the ideal hue. Therefore, it is also possible to reproduce the color of the photo tone two: two on the paper. Further, the ink composition of the present invention does not cause solid precipitation, physical property change, and excellent color stability after a long period of time. When the ink composition of the present invention is used as::: water, the ink composition in the vicinity of the nozzle is also less likely to be dried by drying, and the ejector (recording head) is not clogged. In addition, the present composition does not produce physical properties in the following cases. 7 匕 使用 使用 使用 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Ink jet printer to intermittently: and: the ink composition of the present invention is used for the image of the sfl transfer sheet having the ink receiving layer, and the image is water-repellent and moisture-resistant. Good scratch resistance, light fastness, etc., especially for stability and stability. S. Image of photo tone for a long time. In addition, compared with conventional ink, color development on plain paper and printing density. Excellent in sex, especially in terms of high chroma. In the case of the sample, the water-soluble azo compound of the present invention represented by the above formula (1) and the ink composition of the present invention having the water-soluble azo compound are often useful for various recording inks (4), and (4) for inkjet recording. The use of ink is very useful. [Examples] The present invention will be more specifically described by the following examples, but the present invention is not limited by the examples. Further, unless otherwise specified, "parts" and %" herein are the mass basis and the reaction temperature is the internal temperature. Synthesized. The value obtained by measuring ληι & χ (maximum absorption wavelength) is the measured value in the water solution of Ρ 8 . Further, in each structural formula of the compound obtained in the examples, an acidic functional group such as (d) or an exact group is 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 100 g/L or more at room temperature. 28 201233732 [Example 1] (Step 1) One side was adjusted to pH 6 with sodium hydroxide, and 20.7 parts of 5-amino-2-benzenesulfonic acid was dissolved in 2 parts of water, and then sodium nitrite was added. 72 copies. This solution was added dropwise to 2 parts of 5% hydrochloric acid at 0 to 10 C' for 3 minutes, and then stirred under 10 C 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, 23.1 parts of 2-(sulfopropoxy)aniline was dissolved in 13 parts of water, and 10.4 parts of sodium hydrogen sulfite and 8.6 parts were used. % Formalin, a sulfhydryl sulfonic acid derivative is produced by a conventional method. The obtained mercapto-ω-sulfonic acid derivative was added to the diazonium reaction solution prepared by the first hydrazine, and stirred at 0 to 15 ° C, ρ Η 2 to 4 for 24 hours. After the reaction solution was adjusted to pH 以 with sodium hydroxide, the mixture was stirred at 8 Torr to 95 ° for 5 hours while maintaining the ΡΗ 11 surface, and further sodium sulfate 1 was added for salting out, and the precipitated solid was separated by filtration. Thus, 1 part of a wet cake of the azo compound represented by the following formula (6) was obtained. Ho3s(ch2)3o

Nh2 (6) (Step 2) Adding trimeric chlorination to 250 parts of ice water by adding the product name LE〇c〇LRTM TD90 (surfactant) in 1 part of the company and stirring it vigorously. Cyanide 3.6 parts 'and stirred at 〇~5<t for 3 minutes to obtain a suspension. Then, 100 parts of the wet cake of the compound represented by the above formula (6) is dissolved in water 200.

In the 201233732 portion, the suspension was added dropwise to the solution over a period of 30 minutes. After the completion of the dropwise addition, the mixture was mixed at pH 6 to 8, 25 to 45 for 6 hours. To the resulting solution, 40.0 parts of iminodiacetic acid was added, and it was stirred at pH 7 to 9, and it was stirred for 4 hours. After cooling the obtained reaction solution to 2 () to hunger, 800 parts of acetone was added to the reaction solution, and the mixture was stirred at 2 Torr to 25 ° for 1 hour. The precipitated solid was separated by filtration, whereby a wet cake of 5 〇 was obtained. This wet cake was dried using a hot ho3s (ch2) 3o air dryer of 8 &£>c, thereby obtaining a sodium salt of the water-soluble azo compound of the present invention represented by the following formula (7) (?imax) : 4〇4 〇nm)i3 5 parts.

S03H

(7) H02C—CH 2 —co 2h [Example 2] In place of the use of bis[(4-sulfophenyl)methyl]amine 1 〇 7 1 part, instead of the imidodiacetic acid 4 in the step U) of Example U The water-soluble azo nitride of the present invention represented by the following formula (8) was obtained in the same manner as in Example 1 except for the hydrazine. Sodium salt of the substance 14. 〇 〇 max : 395.0 nm). Ho3s(ch2)3o

(8) h〇3s^

HO3S-Q-CH2 '"CHz-^-S03H 201233732

[Example 3 J] The following procedure was carried out in the same manner as in Example 1 except that 2 parts of 2-(sulfobutoxy)aniline was used, and 2 (2. The hair of the formula (9)

Sodium salt of azo compound 14 5 parts (λη^χ : 4〇i 5 nm) H03S(CH2)40 0(CH?)4S03H Substituted Example 'The rest and the actual water solubility ch^n=n-^I ho3s 〆〇(〇h2)4s ΝγΝγΝ-^^--Ν==Ν

(9)

H02C—CH2 SCH2-<i〇2H

[Examples 4 to 6] (A) Preparation of Ink The azo compound [sodium salt of the formula (7) to the formula (9)] obtained in the above Examples 1 to 3 was used as a dye, and The compositions shown in Table 2 were mixed and prepared into a solution, whereby the ink composition of the present invention was obtained. The test ink was prepared by filtering the obtained ink composition with a membrane filter of 0 · 4 5 μηι to remove inclusions. Further, the pH of the ink for the test is in the range of 8.0 to 9.5. Further, in the following Table 2, the "surfactant" was a product name of Surfynol RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. The preparation of each of the inks using the compounds obtained in Examples 1 to 3 was carried out as Examples 4 to 6, respectively. 31 201233732 [Table 2] ----- Composition of tzK composition • Each compound of the formula - * 例 Example 3.5 俭 Glycerin 5.0 parts ------ Urea 5.0 parts - Ν-methyl-2-. Bilo bites 4.0 parts - § propanol 3.0 parts - butyl carbitol 2.0 parts - surfactants 0.1 parts ------- ion exchange water 77.4 parts - total _ . - y - 100.0 parts [Comparative Example 1] θ was prepared in the same manner as in Examples 4 to 6 except that the compound represented by the formula (10) was replaced by the compound of the present invention obtained in each Example. Compare inks. The preparation of the ink is used as a comparative example. The compound used in the comparative example 1 is disclosed in Japanese Patent Publication No. Sho 55-130-223. This compound can be used in inkjet inks.

32 201233732 [Comparative Example 2] Except that the compound of the present invention obtained in Example 1 of Patent Document 2 was used, in place of the compound of the present invention obtained in each Example, ^, < η Examples 4 to 6 were carried out in the same manner, and the ink for comparison was prepared. The adjustment of this ink was made in Comparative Example 2. The compound of the compound used in Comparative Example 2, and the formula are as shown in the following formula (11). Bu

H03S(CH2)30 0(CH2)3S〇3H

-Ν=Ν·

Vso3h (1)) (ch2)2—so3h [Comparative Example 3] Except for the compound of the present invention obtained by substituting each of the examples in the compound example of Table 1 of Patent Document 2, Examples 4 to 6 were carried out in the same manner, and the ink for comparison was prepared. The modulation of this ink was used as Comparative Example 3. The structural formula of the compound used in Comparative Example 3 is represented by the following formula (12).

H03S(CH2)30 0(CH2)3S03H

(B) Inkjet recording using an inkjet printer (manufactured by Canon Co., Ltd., trade name PIXUSRTM ip45 00) 'The inks prepared in the above Examples 4 to 6 and the respective comparative examples were on 5 kinds of glossy papers ( Inkjet recording is performed on inkjet recording, 33 201233732 As a light resistance test, an ozone gas test, a print density (Dy value) test, and a township* test. In the case of performing ink jet recording, an image pattern having a yellow level is obtained by using a plurality of stages of gradation (darkness level) to obtain a reflection density. The obtained recorded matter was subjected to various tests as a test piece. Glossy Paper 1: Canon Co., Ltd. Product Name: Gloss pr〇 [Platinum Grade] (PT-101) Glossy Paper 2: Canon Co., Ltd. Trade Name: Gloss Gold (GL-lOl) Glossy Paper 3: Seik0 Epson Shares Co., Ltd. Product Name: Photo Paper Crispia (i^Gloss) Gloss, 4 4 · Product Name of HP Co., Ltd. · Advanced Photo Paper (1) (10) ) Glossy Paper 5: Brother Co., Ltd. Product Name: Photo Paper (BP71GA4) The light resistance test and the ozone gas resistance test are performed by measuring the reflection density of the portion of the recorded material having the reflection density D closest to the test. The chroma (C*) and the print density (four) values are the highest positions in the gradient. Determination of chroma and reflection density, using a color measurement system (trade name)

SpectroEye, made by X_nte). The colorimetric system was carried out under the following conditions: The concentration standard was DIN (DeutSche Industrie Nomung c〇l〇ur System), and the viewing angle was 2. Light source D65. The following test methods for δ-loaded recorded images and methods for evaluating test results. (C) Xenon arc lamp light resistance test 34 201233732 Each test piece was placed on a stand and used at a temperature of 24 by using a 氤 soliton weathering tester XL75 [manufactured by Suga Test Machine Co., Ltd.]. 〇, humidity 6〇% RH ' was irradiated for 168 hours with an illumination of 0.3 6 W/m 2 . 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 4 to 6 and Comparative Examples 1 to 3 all showed good results. (D) Ozone gas resistance test An ozone weathering tester, MS-H [manufactured by Suga Test Machine Co., Ltd.], was placed in an environment having an ozone concentration of 1 〇 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 4 to 6 and Comparative Examples 1 to 3 showed poor 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 3 below. 35 201233732 [Table 3] Dy value glossy paper 1 Gloss paper 2 --^ —---- Gloss New Zealand 1 Example 4 1^--- Paper 4 Gloss paper 5 2.11 2.05 2.21 2.01 Example 5 One - * ' J ------ 2.18 1.93 2.05 2.06 ____Κ93 Example 6 ------^ 2.07 2.01 2.09 Comparative Example 1 2.17 1.94 2.01 Comparative Example 2 __L9 1.97 1.85 1.89 1 Qfi Comparative Example 3 _____LJi 1.93 1.77 1.88 ____LS5 1.94 < 1 / Chen (1) y value), in any glossy paper, Comparative Example 2 and Comparative Example 3 both sea-private one 3 · '·' members are not more inferior to the examples 4 to 6 results. (F) Saturation test The yellow chroma C ° results obtained by the above colorimetric system were as shown in Table 4 below for the gradation portion having the highest reflection concentration in each test piece. [Table 4] -- '^ — chroma glossy paper 2 glossy paper 3 ---- glossy paper 4 glossy paper 5 Example 4 111^. 115 118 ----- 110 115 Example 5 109_^ 109 114 106 111 Example 6 --------- UjL^ 107 114 Γ -1 ----·,, 106 111 Comparative Example 1 — · ~ 106,^-- 103 108 101 104 Comparative Example 2 —-- ------- 99 - 1 103 98 ~ - 1 ------- Comparative Example 3 104 106 111 106 108 From the results of Table 4, it is known that in terms of chroma (C* value), in any gloss 36 201233732 Paper 'Comparative Example 2' shows even worse results than Example 6~丨〇. From the results of Tables 3 to 4, the results of Comparative Example i showed the following results: In the yellow printing density (Dy value), the glosses $i and 3 were good, but in glossy papers 2, 4 and 5, Each of the examples is more disadvantageous, and in terms of chroma (C* value), any glossy paper is more disadvantageous than the respective examples. In Comparative Example 2, the following results were obtained: in terms of yellow printing density (color value) and chroma (C* value), any glossy paper was inferior to each of the examples. Comparative Example 3 showed the following results: in terms of chroma (c* value), gloss papers 2 and 4 were good, but in glossy papers 3 and 5, it was worse than the examples, and in the yellow column. In terms of printing density (Dy value), any glossy paper is more disadvantageous than the respective examples. In contrast, each of the examples showed the following results: excellent in all glossy papers in terms of chroma (C* value) and yellow printing density (Dy value) of the recorded matter. Therefore, it is understood that the water-soluble azo compound of the present invention and the ink composition of the present invention containing the same have a high-definition hue and a high yellow printing density value as compared with the conventional dye. Regardless of the type of glossy paper, color rendering is excellent. [Industrial Applicability] The water-soluble azo compound of the present invention having a yellow pigment and the yellow ink composition of the present invention containing the water-based azo compound can obtain a high-color, high-color recording image. . Therefore, the compound and the ink composition containing the same: are very useful for various recording purposes, and are particularly useful for ink jet recording applications. 37 201233732 [Simple description of the diagram] None [Key component symbol description]

Claims (1)

201233732 VII. Patent application scope: • A water-soluble azo compound or a salt thereof, the water-soluble oxime hexa-beta compound. The compound is as shown in the following formula (1): (wherein, X represents an integer of 2 to 4, and an amine group) The hydrazine represents a formula (2) or (3) represented by the following formula (^CH2 - C〇2H, ch2 - co2h ^CH2 in the formula (3) - R (2) (3) R ' R represents a hydrogen atom or a sulfo group. The water-soluble azo compound or a salt thereof according to claim 1, wherein 'in the above formula (1), "3β salt m: The water-soluble azo compound described in the above paragraph 1 or the water-soluble azo compound represented by the formula (丨) is as follows: 39 (4) 201233732 H03S(CH2)3〇 0(CH2)3S03H H03S ΝγΝ ϊ—CHo^C Η〇2〇CH2 UH2—co2h 4. An ink composition containing the water-soluble matter as described in any one of claims 1 to 3. An azo compound or a salt thereof. 5. The ink composition of claim 4, wherein the ink composition further comprises a water-soluble organic solvent. 6. The ink composition of claim 4, which is for ink jet recording. : a Ribbin ink recording method, which uses the ink composition as described in claim 4 of the patent application or φ as the ink, and causes the ink droplets of the ink to be "attached to the recorded signal according to the recording signal". The material is recorded for recording. 8. The material to be recorded as described in item 7 of the patent application is a sheet for information transmission. The recording method, wherein '9·If the patent application scope is 8th, the aforementioned information transmission sheet is ordinary = recorded The method 'wherein, or 疋 has an ink receiving layer 40 201233732 material', the ink receiving layer contains a porous white inorganic substance 10.: coloring body, which is colored by any of the following: :) The water-soluble azo compound according to item 1 of the patent application or (b) the ink composition containing the water-soluble azo compound as described in the scope of the patent application or the formula 1; An ink composition of the water-soluble azo compound-/, now and a water-soluble organic solvent as described in claim 1 of the patent application. The color body of the invention is by the saint 5 as described in claim 7 Recorded method 12 ^ Inkjet printer ' is filled with a container containing the ink composition of the monthly patent $ & 4 item. Such as Shen 41 201233732 III, English abstract: No four (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: