TW201231566A - Water-soluble azo compound or salt thereof, ink composition, and colored object - Google Patents

Abstract

The purpose of the present invention is to provide: a water-soluble yellow colorant (compound) which is highly soluble in water, has high color-developing properties, and gives recorded images having an excellent chroma; and a yellow ink composition which contains the colorant and is for use in various kinds of recording, in particular, ink-jet recording. The colorant is a water-soluble azo compound represented by formula (1) or a salt thereof. The ink composition, which contains the compound or salt, has high color-developing properties, has a chroma and a hue that are suited for ink-jet recording, gives recorded matter having high fastness properties of various kinds, and gives recorded images that are excellent in terms of storage stability or the like. In formula (1), x is an integer of 2-4, and group A represents an amino group represented by any of formulae (2) to (6). In formula (2), w is an integer of 2-6. In formula (3), v is an integer of 1-3.

Description

201231566 6. Technical Field of the Invention: The present invention relates to a water-soluble disazo compound (disaz〇compound) or a salt thereof; an ink composition containing the azo compound or a salt thereof; Wait for the color to be colored. [Prior Art] Among the various shirt color recording methods, one of the representative methods has been developed, and various ink ejection methods have been developed using the ink jet printer recording method. In some of the methods, droplets of ink are generated and attached to various recording materials (paper, film, cloth, etc.) for recording. In this method, since the recording head and the material to be recorded are not in direct contact with each other, the sound is less likely to be generated, and the method is characterized in that it is easy to realize miniaturization, high speed, and colorization. Therefore, it has been rapidly popularized in recent years, and it is expected in the future. Substantial growth. ^, 8 In the ink as a pen or a signature, the ink is prepared by dissolving a water-soluble and accommodating pigment (dye) in an aqueous medium. These aqueous inks are added with a water-soluble organic solvent to prevent clogging of the ink in the nib or ink ejecting spray. And, for the ink, it is required to give the concentration, the clogging in the nozzle, the image recorded in the second recording, the dryness of the pen tip or less and the wide-area recording material, and the oozing age/ And to preserve the excellent performance of t疋.萆The nozzle of the inkjet is clogged, and the pigment is solidified and precipitated due to the moisture in the ink being evaporated in the mouth of the nozzle 201231566, which is less than the solvent or the additive. . Therefore, even in the state where the amount of water in the ink is small, solids are not easily precipitated, and it is very important to require performance. For this reason, the high solubility for solvents or additives is also the property required for pigments. Further, a method of solving nozzle clogging is known as a method of using a pigment having a high printing density. By using the pigment 'm having a high printing density, the pigment content in the ink can be reduced while maintaining the conventional material concentration. Not only does it make it difficult to precipitate the pigment, but it is also advantageous in terms of cost, and therefore it is desired to develop a pigment having a high printing density. . However, by using an inkjet printer to record image or text information on a computer's color display in color, it is usually used by yellow (", magenta (Μ), cyan (C), black (κ) The sub_tive color mixture of the four-color ink 'by this, the image is recorded in color. In order to subtract the mixed image as much as possible, the CRT (Braun tube) display, etc., is reddue as much as possible. (addive c〇i〇r mixture) image of (R), green (g), and blue (B), which are used for each pigment of the ink and especially γ, M, and C, are expected to be close The hue of the standard color is vivid. The so-called vividness here generally means that it has a southern chroma. When using the three primary colors of γ, M, and c with low chroma, there may be a single color or /3⁄4 color. The color gamut becomes narrow and the range of the color gamut to be expressed becomes insufficient. Therefore, it is desired to develop a pigment having high chroma and an ink containing the pigment. Further, the performance of the ink is required for long-term storage. Stability, high concentration of recorded images, Moreover, the image has excellent water resistance, moisture resistance, transparency such as 201231566 light resistance, gas resistance, etc. The term "gas resistance" as used herein refers to impurities which are present in the air and have oxidation. The acting gas (also called oxidizing gas) reacts with the pigment (dye) of the recorded image on the recorded material or in the recorded material to change/fade the recorded image. In the oxidizing gas, In particular, ozone gas is considered to be the main reason for promoting the change/fade phenomenon of ink-jet recorded images. (4) In view of this change, the fading phenomenon is a characteristic phenomenon for ink-jet recorded images, and therefore, resistance The improvement of ozone gas is an important technical problem in this field. Due to the development of inkjet technology in recent years, the speed of inkjet recording (printing) is very significant. Therefore, with the use of electronic toner (eiee_ic t_r) ^ Lei The same applies to the main use in the office environment, that is, for the printing of documents on plain paper, the market tends to use inkjet printers. The inkjet printer has no choice to remember. The type of paper and the low cost of the printer itself, especially in the small to medium-sized office environment such as S0H0: Small 〇ffiee H〇me O ffi ce. When printing on paper, the inkjet printer is used to emphasize the hue, color (printing) density, and water resistance among the qualities required for printed matter. Based on the goal of satisfying these properties, A method of using a pigment ink is proposed. However, the pigment ink is not in a solution state because the pigment is not dissolved in the aqueous ink, and the ink in a dispersed state is used for spraying. In the case of ink recording, there is a problem that the stability of the ink itself or the nozzle of the recording head is clogged. Moreover, when using pigment inks, problems often occur in abrasion resistance. When using dye ink, it is considered to be less prone to such a problem. 201231566 'But especially in terms of water resistance, the bottle is very inferior to pigment ink, so it is strongly expected to be right. & This is broken, and the dye ink and the pigment black water are not enough to penetrate the pigment on the surface of the plain paper by the inkjet (10) and quickly penetrate the problem of the father. The method of providing an ink-receiving image for obtaining a photo-quality image quality is preferable to a method of providing an ink-receiving layer on a surface of a recording material. An ink receiving layer provided for such a purpose, inflammation In order to accelerate the drying of the ink and reduce the pigmentation of the pigment in the image quality, most of the layers have a white inorganic mineral. However, in such a recorded material, the above can be particularly noticeably observed. Due to the change in ozone gas/visual color. Due to the popularity of recent digital cameras and color printers, the chances of printing images obtained by digital cameras, etc., into photo-quality image quality have increased in the home. The above-mentioned recording image change/fading due to oxidizing gas is regarded as a big problem. Compared with the other three primary colors, namely magenta or cyan, light yellowness has been proposed for the yellow pigment and has good oxidation resistance. Gas-tolerant pigments. However, there is currently no yellow pigment or yellow inkjet recording inkjet recording that satisfies the market requirements for high sharpness and various firmness. Water. A yellow pigment for inkjet which is excellent in water solubility and vividness, and CI (dye index: Co丨or Index) direct yellow 132. Further development of yellow pigment for inkjet recording in recent years. Several kinds of azo-based dyes having high fastness have been proposed. Patent Document 1 discloses a yellow anionic azo compound which is resistant to light and to water. 7 201231566 Patent Document 2 discloses - It has high solubility in water and the right kind of water-only azo compound 's. It has moisture resistance, ozone gas resistance and light resistance and can not afford 'a kind of yellow water-soluble azo It has high solubility in water and has good physical properties, such as ozone gas resistance, excellent resistance to light, light resistance, light resistance, and water resistance. In Document 4, it is revealed that -, dragon species water / combined 1 ± @ color pigment, its solubility for water or water-soluble organic solvents is ancient, round you & solution, image print density is high and image Excellent in light and ozone resistance. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei-4-233975 (Patent Document 2) JP-A-2006-1 52264 [Patent Document 3] International Publication No. 20〇9/〇66412 [Patent [Document 4] International Publication No. 2010/125903 [Draft 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 pigment. The dye has high solubility in water, and the recorded image has high color rendering property (printing density) and is excellent in chroma, and the yellow ink composition is used for various recordings, particularly for inkjet recording. 8 201231566 [Solution In order to solve the above problems, the inventors of the present invention have diligently studied and found a characteristic water-soluble compound of the following formula (1) and contains The ink composition of the chemical composition can solve the above problems, thereby completing the present invention. That is, the present invention relates to the following invention. 1) A water-soluble azo compound or a salt thereof, which is represented by the following formula (丨):

H03S(CH2)x0 0(CH2)xS03H

(1) (wherein 'X represents an integer of 2 to 4, and the base A represents an amine group represented by any one of the following formulas (2) 5), (2) (in the formula (2), w represents 2 To the integer of 6),

-1<H (3) (CH2)v-CH3 ), V represents an integer from 0 to 3) 乂, Η3 η3(/ \η3 (4) Η

Nch2—ξϊ /CH2—co2h %h2~C02H (5) (6) 201231566 or a salt thereof, wherein 2) the water-soluble azo compound according to the above 1), wherein X in the above formula (1) is 3. The water-soluble azo compound or a salt thereof according to the above formula (1), wherein the water-soluble azo compound represented by the above formula (1) is as defined in the following formula (7)

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), which further contains a water-soluble organic solvent. ό) the ink address product of the above 4) is used as an inkjet recording method for inkjet recording, and the ink composition according to the above 4) is used as an ink, and The ink droplets of the ink are ejected on the recording material according to the recording signal to be recorded. The inkjet recording method according to the above 7), wherein the material to be recorded is a sheet for information transmission. The inkjet recording method according to the above 8), wherein the information transfer sheet is plain paper or a sheet having an ink receiving layer, and the ink receiving layer contains a porous white inorganic material. 10 201231566 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 a ruthenium as described above An ink composition of the water-soluble azo compound or a salt thereof; and (c) an ink composition containing the water-soluble azo compound or a salt thereof as described above and a water-soluble organic solvent. U) - a coloring body which is colored 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. [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 ink composition of the present invention containing the compound or a salt thereof In the course of the object, for example, the filterability of the film passer is good. Further, the image recorded by the ink composition of the present invention containing the compound of the present invention is excellent in print density and chroma compared to the image recorded using the conventional compound. Therefore, the azo compound of the present invention represented by the above formula (1) or a salt thereof, and an ink composition containing the azo compound or a salt thereof are used for various inks for recording, and particularly for inkjet recording. It is extremely useful for ink use. [Embodiment] Hereinafter, the present invention will be described in detail. The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof 11 201231566 is a water-soluble yellow pigment. In the present specification, as long as there is no special explanation, the acidic functional groups such as the base and the slow base are a, ,;: she lacks & ^ & This is expressed in the form of free acid. Further, as described above, the present invention contains both a water-soluble azo compound or a salt of the compound which is not supported by the above formula c 1 ), but often both are referred to as "compounds or salts thereof" and the like. It will be too complicated. So for the sake of convenience, as long as there is no

In particular, the "water-soluble azo" compound of the present invention will be briefly described below, including "λ益_ aB + γ υ A (water-soluble azo) compound of the present invention or a salt thereof". "." The above formula (1) The compound of the present invention is represented by the above formula (丨), wherein 'X represents an integer of 2 to 4, and more preferably 3. In the above formula (1), the group A represents an amine group represented by any one of the above formulas (2) to (6). w in the middle represents an integer of 2 to 6, and 2 v represents an integer of 0 to 3, preferably 〇. Here, the above formula (2) is preferred. Further, in the formula (3), the amine group represented by the formula (2) or the amine group represented by the above formula (6) is preferable. Among the above-mentioned bases A, it is preferred to combine the compounds which are preferred, and more preferably a compound which is preferably combined. The same is true for the combination of the better and the better. A preferred compound of the above formula (1) is a compound represented by the above formula (7). In addition to the present invention represented by the above formula (1), the compound can be produced, for example, in the following manner. In addition, the following formula (AA) to φ嗝a shelter m

The bases A, V, W, and X which are appropriately used in the main body have the same meanings as the bases A, v, w, and 12 201231566 x in the above formula (1), respectively. The compound of the following formula (AA) obtained by using a commercially available 2-amino group as a raw material is converted into the sulfhydryl group represented by the following formula (B) using sodium hydrogen sulfite and formalin. -ω - acid derivative. Next, the 5-amino-2-chlorobenzoic acid represented by the following formula (C) is diazotized in a usual manner, and then at the reaction temperature, ρ Η 2 to 4, and the previously obtained formula (Β) The methyl-omega-sulfonic acid derivative shown is subjected to a coupling reaction, and then a hydrolysis reaction is carried out at a reaction temperature of 80 to 95 ° C and a pH of 10.5 to 11.5 to obtain a compound represented by the following formula (D). Further, the present synthesis is a method in accordance with the method described in Japanese Patent Publication No. 2006-152264.

H〇2c_ (c) On H03S(CH2)x〇

Next, the compound represented by the above formula (D) (2 equivalents) and a trimeric cyanogen halide (1 equivalent), for example, with trimerized cyanide (1 equivalent) at a reaction temperature of 15 to 45 ° C, pH 5~ Condensation is carried out at 8 to obtain a compound represented by the following formula (E)

H03S(CH2)x0 〇(CH2)xS〇3H ci^p-1 ho2c

H - H (E) 13 201231566 and the obtained gas atom of triazine in the compound represented by the above formula (E), at a reaction temperature of 75 to 9 Torr, pH 7 to 9 The compound of the present invention represented by the above formula (1) can be obtained by using an amine represented by any one of the following formulas (F) to (J).

/ΗΗ—< N(CH2)w-〇H (F) /H , (CH2)v-CH3^v0"3 \η3 h-n, H2—(G) (H) (I)

/CH2~C02H ^οη2 - οο2η (J) The amine represented by the above formula (F) includes the following specific examples: Aminoethanol, 3-Aminopropanol, 4·Aminobutanol, and 5 Amine Base, 6-aminohexanol, and the like. Further, the amine represented by the above formula (G) includes the following specific examples: methylamine, ethylamine, n-propylamine, n-butylamine and the like. . The amine represented by the above formula (H) can easily obtain an amine represented by the above formula (1), which is commercially available as a tertiary butylamine, and can be easily obtained as a commercially available product of 20 milamine. Further, as the amine represented by the above formula, a commercially available product of iminodiacetic acid can be easily obtained. Specific examples of the compound of the present invention represented by the above formula (1) are shown in the following Tables 1 to 3', but the present invention is not limited to these specific examples. Further, in 201231566, in Tables 1 to 3 below, the bases a, v, w, and χ correspond to v, w&x in the above formula (1) or the base A. The compound Nos. 1 to 7 are specific examples when the group a is an amine group represented by the above formula (2), and the compound number 8 to 丨i,

Specific examples of the case where the base A is an amine group represented by the above formula (3), and the compound 12 is a specific example when the base A is the above-mentioned, and the compound of the formula () is not a compound of the formula (3). The sulfhydryl group A is a specific example of the above formula (5, Zhang-^ « compound No. 14, which is the agricultural A a ). When flying (6) does not have an amine group 15 201231566 [Table l]

Compound number structure XWV 1 2 2 ho3s(ch2)2o < Η〇2〇^ ΗΝ X(CH; D(CH2)2S03H Qn=nQ^ci co2h >) 2-〇H 2 3 2 ho3s(ch2) 3o c Ch-pN^HQ-N^N^NH H02C ΝγΝ HN (CH2 j)(CH2)3S03H 3-n=nQ-ci co2h )2-〇H 3 4 2 H03S(CH2)40 c η〇2〇 ~^ ^γΝ HN , (ch2 )(CH2)4S03H 3-n=nQ-ci co2h )2-〇H 4 3 3 ho3s(ch2)3o CI-QN=N-0-N^flYN-j H02C ΝγΝ HN '(ch2) )(CH2)3S03H 3-n=nQ-ci co2h 3-oh 5 3 4 H03S(CH2)30 0(CH2)3S03H ΜίίΗ〇^Ν=ΝΗΠκ〇Ι H02C ΝγΝ C02H HN N(CH2)4 -〇H 16 201231566 [Table 2] Compound No. Structural Formula XWV 6 3 5 H03S(CH2)30 0(CH2)3S03H H02c ΝγΝ C02H HN N(CH2)5-OH 7 3 6 ho3s(ch2)3o 〇(ch2 3so3h CI-QN=N-^Hg nyn-0-n=nQ-ci H02C ΝγΝ C〇2H HN ,(CH2)6-〇H 8 3 0 H03S(CH2)30 0(CH2)3S03H ci-^n ^hQ^ ntn-Qn=nQ-ci H02C ΝγΝ 〇 2H HN ch3 9 3 1 H03S(CH2)30 0(CH2)3S03H CI-^-N=N-^N^NYN-^-N=N-^ -CI H02c ΝγΝ C02H HN Hzfc—CH3 10 3 2 H03S(CH2)30 0(CH2)3S03H Ch-QN^^Q4J NrN-^^=NQ-CI H02C ΝγΝ C02H HN , (ch2)2-ch3 17 201231566 [table 3]

Compound number structure XWV 11 3 3 ho3s(ch2)3o 0(CH2)3S03H ho2c fly o2h HN \CH2)3~CH3 12 3 1 — H03S(CH2)30 0(CH2)3S03H 〇Η-ρ-Ν= Ν-^4ί KyN-QN=N-〇-C| H〇2〇ΝγΝ C〇2H H\/CH3 η〆\h3 13 3 ho3s(ch2)3o 0(CH2)3S03H ci-O^^-041 ^ N-0-n=nQ^i ho2c b〇2H HNV 14 3 ho3s(ch2)3o ?(ch2)3so3h ci-^^n-^4Ixkyn-0-n=n-〇-ci Η〇2〇ΝγΝ ^ C〇2H ho2c-h2c^ \; H2-C02H The compound represented by the above formula (1) is also present as a bear of the free acid or a salt thereof. The salt of the compound represented by the above formula (1) may, for example, be a salt with an inorganic or organic cation. Specific examples of the salt with the inorganic cation include a salt of an alkali metal salt such as a lithium salt, a sodium salt or a potassium salt; and a salt of an ammonium salt (NH 4 '+) and an organic cation, and specific examples thereof include cations. The salt of the fourth grade shown in the formula (8 18 201231566) is 'but is not limited to these.

In the above formula (8), 'Z1 to Z4 each independently represent a hydrogen atom, a C4 alkyl group, a hydroxy group C to C4 alkyl group, or a hydroxy group C1 to C4 alkoxy group C1 to C4 alkyl group, and at least one of z1 to Z4 is a group other than a hydrogen atom. Here, examples of the C1 to C4 alkyl groups in Z1 to Z4 include a methyl group and an ethyl group. Similarly, examples of the above-mentioned hydroxy c丨 to C4 alkyl group include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 4-hydroxybutyl '3·hydroxybutyl group. 2-hydroxybutyl group and the like. Similarly, examples of the above-mentioned light-based C1 to C4 pendant oxy-C1 to C4-based groups include ethoxymethylmethyl group, 2-hydroxyethoxyethyl group, and 3 (hydroxy ethoxy group). Propyl, 3-(hydroxyethoxy)butyl, 2-(hydroxyethoxy)butyl, and the like. Among the above salts, the following are preferred: alkali metal salts such as sodium, potassium, and lithium salts, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine salts. Organic four-level salt; (four) and so on. Preferred among these are bell salts, sodium salts, and ammonium salts. As will be understood by those of ordinary skill in the art, the salt or free acid' may be, for example, a salt or the like of the compound represented by the above formula (1) in the above formula (丨). Easy to get. For example, for the reaction liquid after the end of the final step in the synthesis reaction after the final step in the synthesis reaction,

b, for the reaction liquid after the completion of the step of the compound represented by the above formula (1), or the method of adding a chlorination method by adding a chlorination method of, for example, a method of adding a π π bath organic solvent thereto, Filtration and Separation of 19 201231566 Solids 'The salt of the compound represented by the above formula (1) can be obtained by the form of the wet cake. Further, after dissolving the obtained wet salt of the sodium salt in water, an acid such as hydrochloric acid is added to adjust the pH thereof, and the precipitated solid is separated by filtration, whereby the free acid of the compound represented by the above formula (1) can be obtained. 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. Further, after the obtained wet cake of the sodium salt or the dried solid thereof is dissolved in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added thereto to appropriately adjust the pH to, for example, pH 1 to 3' and then filtered. The precipitated solid is separated, whereby a salt of the compound represented by the above formula (1) can be obtained. By appropriately adjusting the amount and/or pH of the added vaporized ammonium, a mixture of the ammonium salt of the compound represented by the above formula (1) and the sodium salt of the compound represented by the above formula (1) can also be obtained. Or a mixture of a free acid and an ammonium salt of the compound represented by the above formula (丨). Further, as will be described later, a mineral acid (e.g., hydrochloric acid, sulfuric acid, or the like) may be added to the reaction liquid after completion of the above reaction to directly obtain a solid of a free acid. At this time, the wet cake of the free acid of the compound represented by the above formula (1) is added to water and mixed, and then added, for example, a hydroxide clock, a hydrogen peroxide, ammonia water, or the above formula (8). The salt of the organic quaternary ammonium hydroxide or the like is subjected to salt-forming, and a potassium salt, a lithium salt, an ammonium salt, a quaternary ammonium salt or the like corresponding to each of the added compounds can also be obtained. By limiting the number of moles of the above-mentioned nitrogen oxides added to the molar number of the free acid, it is also possible to prepare, for example, a mixed salt of a lithium salt and a sodium salt, and further to prepare a lithium salt, a sodium salt, and a mixed salt of an ammonium salt or the like. The 20 201231566 salt of the compound represented by the above formula (n) may have physical properties such as solubility due to the type of the salt or ink performance when used as an ink. ^, preferably ink properties according to purpose The type of the salt is selected. 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, or can be obtained by dissociating the obtained salt. The acid solid is washed with water or acidic water such as hydrochloric acid water to remove 'inorganic salts (inorganic impurities) contained as impurities, such as sodium carbonate or sodium sulfate. The compound of the present invention obtained as described above. The free acid, as described above, can be obtained by treating the obtained wet cake or its dried sift in water with a desired inorganic or organic test to obtain a salt of the corresponding compound. : cerium hydroxide, sodium hydroxide, hydroxide, etc., metal argon oxide; carbonic acid chain, sodium carbonate, potassium carbonate and other metal hydroxide; hydrogen hydroxide (teaching water) and so on. For example, the organic amine corresponding to the fourth order of the above formula (8), for example, an alkanolamine such as diethanolamine or triethanolamine, etc., is used, but is not limited thereto. The compound of the present invention, It is suitable for the dyeing of natural and synthetic fiber materials or blends, and is also suitable for the production of writing inks and ink compositions for inkjet recording, for example, in the final step of the synthesis reaction of the compound of the present invention represented by the above formula (1). The reaction liquid after the completion may be used as it is in the production of the ink composition of the present invention. However, it may be obtained by, for example, drying the reaction liquid or the like by the above method or spray drying to separate the compound. The compound of the present invention is processed into an ink composition. The ink composition of the present invention is a mixed solution machine solution in which the compound 21 201231566 represented by the above formula (1) is dissolved in water or a water fish chopping agent (mixed with water). For those obtained by the organic solvent-soluble preparation, the medium J) 'when the machine ink is added as needed, it is preferred to use the ink as an inkjet printer, the inorganic impurities, A composition was qe fishing e.g. chloride, or two ❹: 3 Some vaporized metal cation ...... e.g. sodium sulfate and the like. At this time, the total content of sodium chlorinated sodium chloride, for example, the total mass of the product, is 5% by mass of the compound U of the formula (1), and the lower limit is 0% by mass. The detection limit may be as follows. The method for producing a small amount of inorganic impurities is, for example, a conventional reverse osmosis membrane: a method of ''or a dry product or a wet sputum of the compound of the present invention. The cake is added to, for example, a water-soluble organic solvent such as a residual or C1 to C4 octanol (for example, alcohol, ethanol, or isopropyl alcohol) or a water-soluble organic solvent, followed by suspension purification or crystallization. The desalting treatment or the like can be carried out by these methods. The ink composition of the present invention contains the above formula (i.e., usually 1 to 20% by mass, preferably 1 to 1% by mass, preferably 2 to 8% by mass, based on the total mass of the ink composition)丨) The compound shown. The ink composition of the present invention is prepared by using water as a medium, and suitably contains a water-soluble organic solvent or an ink preparation agent as needed within the range which does not impair the effects of the present invention. The water-soluble organic solvent sometimes has a function as a dissolving dye, prevents the composition from drying (maintaining a wet state), adjusts the viscosity of the composition, promotes penetration of the dye into the material to be recorded, and adjusts the surface tension of the composition, and the composition 22 201231566 The effect of defoaming or the like is preferable, and therefore, it is preferred to contain a water-soluble organic solvent in the ink composition of the present invention. As an ink preparation agent, for example, an antiseptic and antifungal agent, a pH adjuster, a chelating agent, an anti-recording agent, an ultraviolet absorber, a viscosity adjuster, a dye dissolving agent, an anti-fading agent, a surface tension adjusting agent, and a consumer can be mentioned. A conventional additive such as a foaming agent. The content of the water-soluble organic solvent is from 0 to 60% by mass, preferably from 10 to 50% by mass, based on the total mass of the ink composition of the present invention, and the ink preparation is from 0 to 20% by mass. /. It is better to use 〇~15% by mass. In the ink composition of the present invention, the remainder of the compound represented by the above formula (1), the water-soluble organic solvent, and the ink preparation agent is water. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol; and C4 ani alcohol; N, N• Dimethylcarbendazim, N,N dimethylethene and other amines; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl 2_pyrrolidone, 1,3 -heterocyclic ketones such as dinonyl imidazolidine-2-one, anthracene, 3-dimethylhexahydropyrimidin-2-one; lysine, methyl ethyl ketone, 2-methyl-2-hydroxy-2-keto 4; ketone and other ketones or keto alcohol; tetrahydrofuran, dioxane (di〇Xane) and other cyclic ether; ethylene glycol, I,? · or 1,3-propanediol, 1,2- or 1,4-butanediol, hydrazine, 6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, $2 Alcohol, polypropylene glycol, thiodiglycol, etc., a mono-, oligomeric or polyalkylene glycol or thioethyl alcohol having a C2~C6 alkylene unit; a triterpene glycerin, glycerol, hexanetriol, etc. (three-fold alcohol is preferred); ethylene glycol monothiol scale, ethylene glycol monoethyl ether, ethylene glycol monomethyl hydrazine, diethylene glycol monoethyl (tetra) 23 201231566 butyl carbitol) Triethylene glycol monomethyl ether, ethyl bond; - butane monoethyl alcohol monoethyl shouting and other monoesters of polyol; dimethyl sub-grinding. In the above water-soluble organic solvent, for example, a substance which is solid at normal temperature, such as tri-propylidene propane, is also included. However, these substances have the same effect as the solid i is water-soluble and the aqueous solution containing the material exhibits the same properties as the water-soluble organic solvent, and the same effects can be expected by using these materials. Therefore, in the present specification, for the sake of convenience, even if such a solid substance is expected to be used in the same manner as described above, it is included in the category of a water-soluble organic solvent. The above water-soluble organic solvent is preferably as follows: isopropyl alcohol, glycerin, monoethyl alcohol, diethylene glycol, triethylene glycol, dipropylene glycol, 2-pyrrolidone hydroxyethyl-2-oxaridone, N_mercapto-2-pyrrolidinone, trishydroxypropyl propyl ketone, and butyl carbitol, preferably: isopropanol, glycerol, diethylene glycol, 2-pyrrolidinium, N-methyl _ 2 • Pyrrolidone, and butyl carbitol. The two water, the gluten organic solvent may be used singly or in combination. Examples of the antiseptic and antifungal agent include an organic sulfur system, an organic nitrogen sulfur organic dentate system, a haloallyl code system, a hard propyl group, a fluorene thiol group, and a benzothiazole ( Benz, thiaz 〇 (4), nitrile, acridine, 8 土 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 a quaternary ammonium salt system, a triazine system, a thiacliazine system, an indoleamine (Chongchuan (4) system, an adamantane system, a dithiocarbamate system, a ketone) 〇m〇indan〇ne), a compound such as benzyl bromoacetate, an inorganic salt system, etc. The organic dentate compound is, for example, 24 201231566, which is pentadene, and the 定d oxygen compound is, for example. It can be exemplified by 7::1 and 1 iso-oxygen: the sodium salt of the compound, the iso-(4-) compound, the preparation of 0 肀 thiathiazoline-3-鲷, s chloro-2-methyl _4_isothiazolene servant Zhao " 5 Gas · 2 · methyl 4-isothiazolin-3-one: magnesium, ... methyl ... salic · 3, chlorine (tetra), 2 - methyl _4_ Lin _3, chlorinated. Other antiseptic and mildew The agent can be exemplified by Metric I: sodium benzoate, etc., and further The name of the business name is pr〇xelRTM GXT 疒Q, +, η _ ^XL (S) 4 Pr〇xelRTMXL 2 (s additionally '4 trademarks in this manual. It means that the registration is based on the purpose of improving the stability of the ink preservation. The purpose of the raw material is as a pH adjuster. As long as the pH of the ink can be controlled within the range of 6.0 to U.〇, it can be used. Examples of the material include, for example, diethanolamine, triethanolamine, and the like: an amine; a hydrogen peroxide, a sodium hydroxide, a potassium hydroxide, or the like; and an alkali metal carbonate such as sodium hydride or potassium citrate; ; amine sulfonic acid, such as taurine, etc. As a chelating agent, for example, jujube J. Disodium edetate, sodium nitrotriacetate, sodium hydroxyethylethylenediamine diacetate, diamethylene Sodium amine pentaacetate, sodium uracil diacetate, etc. Acid sulfite, thiosulfate propyl alcohol, pentaerythritol tetranitrate as a rust inhibitor, for example, sodium, ammonium thioglycolate, nitrous acid diacetate, or Dicyclohexyl nitrous acid, etc. As an ultraviolet absorber, examples ^ ^ group, „ 』 A benzophenone compound, a stupid triazole compound, a cassia compound, a triazine 25 201231566 compound, a stilbene compound, and a (benzoxaz〇ie) compound may be used. The compound which uses the absorbing UV light of the stupid Π Π 仆 仆 & & amp 吸收 吸收 吸收 发出 发出 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物Other than the water-soluble organic solvent, for example, polyvinyl alcohol, hexaphyrin, polyamine, polyimine, and the like can be mentioned. Ye Yujing As a dye-dissolving agent, for example, urea, ε-hexine, and carbonic acid. Among them, urea is preferred. * 使用 Use for the purpose of improving image retention. As the anti-fading agent, various organic τ and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydrogen awake, oxykine-aged, di-oxygenated oximes, anthraquinones, stupid amines, amines, sulfonoids, chromanes, and burns. An anilide, a heterocyclic or the like. Examples of the metal complex include a nickel complex, a zinc complex, and the like. The surface tension adjusting agent may, for example, be a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. Examples of the anionic surfactant include an alkyl sulfocarboxylate, an α-thin salt, a polyoxyethylene acetate (p〇ly〇Xyethyiene & 1|^1 ether acetate), and N- Mercapto-amino acid and its salt, N-glycosyl sulfonate, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, Castor oil sulfate, lauryl sulfate, alkylphenol phosphate, alkyl phosphate, alkyl aryl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate , Dioctyl 26 201231566 Jiji succinate and so on. As a cationic surfactant, it is a derivative of a 2-(Ethylene-based hydrazine-based deuterated derivative, a poly(4-ethylene group) π-definite). As an amphoteric surfactant, it can be extracted. Lauryl dimercaptoacetic acid betaine, 2-alkyl_N-mercaptomethyl-w-ww, N-Zhao-ethyl-imidazoline rust betaine, coconut oil fat Amidoxime-methyl I π la & monomethylaminoacetate betaine, polyoctyl polyaminoethylglycine, imidazoline derivatives and the like. Examples of the nonionic surfactant include polyoxyethylene phenyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene sulfonate, and poly Oxyethylene lauryl bond, polyoxyethylene bromide, etc.; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbus Alcoholic anhydride monooleate, sorbitol needle sesquioleic acid vinegar, oxyethylene single oil (four), polyoxygenated stearic acid vinegar, 2,4,7,9-tetramethyl-5 -decyne-4,7-diol, 3,6-dimethyl-4_

Acetylene glycol (alcohol) such as octyne-3,6-diol and 3,5-dimercapto-1-hexyn-3-ol, trade name Surfyn〇lRTM 104 manufactured by Rik Chemical Industry Co., Ltd. , 82, 465 '01fineRTM STG, etc.; TGMA-ALDRICH company's TergitolRTM 15-S-7. Examples of the antifoaming agent include a highly oxidized oil system, a glycerin fatty acid ester system, a fluorine system, and a polyoxonium compound. These ink preparation agents can be used singly or in combination. Further, the surface tension of the ink cartridge of the present invention is usually 25 to 70 mN/m, preferably 2 5 to 60 mN/m, and the viscosity is preferably adjusted to 30 mPa·s or less, preferably 2 Å. mPa • s or less. 27 201231566 In the production of the ink composition of the present invention, the order in which the additives and the like are dissolved is not particularly limited. Water for modulating the ink composition is preferably water having less impurities such as ion-exchanged water or steamed water. Further, after the ink composition is prepared, it is also possible to perform precision filtration using a membrane filter or the like as necessary to remove the foreign matter in the ink composition. In particular, when the ink composition of the present invention is used as an ink for inkjet recording, it is preferred to carry out precision filtration. The pore size of the filter used for precision filtration is usually 丨~〇^μιη, preferably 0.8 to 0.1 μηη. An ink composition containing the compound of the present invention is suitable for use in printing, copying, marking, writing, drawing, printing, or recording (printing), and particularly inkjet recording. Further, the ink composition of the present invention is such that the solidification of the vicinity of the nozzle of the recording head of the ink jet printer is not likely to occur, and for this reason, the recording head is not liable to cause clogging. The following method can be exemplified as a method of recording on a material to be recorded by the ink jet recording method of the present invention. That is, a container filled with the ink composition of the present invention is loaded at a predetermined position of an ink jet printer, and the ink composition of the present invention is used as an ink, and ink droplets of the ink are ejected and attached to the image according to a recording signal. Record the material for recording. The ink jet printer can be, for example, a piezoelectric machine (piez〇 electric type) that uses mechanical vibration, and a printer such as a Bubble Jet (registered trademark) method that uses air bubbles generated by heating. The ink jet recording method of the present invention can be used in any manner. There are also cases where a high-definition recorded image is obtained, and two inks containing the same dye are loaded in the same ink jet printer. The difference between the two 28 201231566 inks is the content of the pigment, one is a high pigment ink, and the other is a low pigment ink, which is used as an ink set to make the ink composition of the present invention. It can also be used as such an ink set. Alternatively, the ink composition of the present invention can be used in the ink set, and the conventional ink (composition) can be used. The ink composition of the present invention may be formed into a yellow ink composition containing the compound of the present invention and a conventional yellow pigment, for the purpose of not finely adjusting the range β of the effect obtained by the present invention, based on the purpose of fine-tuning the hue thereof. Further, the compound of the present invention may be used in combination with a magenta coloring matter or a coloring pigment based on the purpose of modulating the coloring of other colors such as black ink or modulating red ink or green ink. Moreover, it is also possible to use a magenta, cyan ink together with the ink composition of the present invention, or to use green, M (or purple), red, black, etc., as needed, for the purpose of obtaining a full-color recorded image. ink. At this time, each color ink is filled in the respective containers. These containers are loaded in a predetermined position of the ink jet printer and used for inkjet recording. The material to be recorded used in the inkjet recording method of the present invention may be, for example, a sheet for information transmission such as paper or film, a fiber or cloth (cellulose, nylon, wool, etc.), a base for leather, or a color calender. Materials, etc., are better for information transfer sheets. The sheet for information transfer is not particularly limited, and plain paper can of course be used. 'A surface-treated one can also be used. Specifically, a sheet obtained by providing an ink receiving layer on a substrate such as paper, synthetic paper or film. Wait. The ink receiving layer 'is a layer having an effect of absorbing ink to accelerate drying thereof. The ink receiving layer is provided by the following method, for example, a method of impregnating or coating a cationic polymer on the above-mentioned base 29 201231566; A method of simultaneously applying a hydrophilic polymer such as a pigment which can absorb a pigment in an ink to a surface of the substrate by a hydrophilic polymer such as a polyethylene glycol or a polyglycol. The material of the inorganic fine particles of the dye in the above-mentioned absorbable ink may, for example, be porous silica dioxide, oxidized sol, or special ceramics. Such a sheet for information transfer having an ink receiving layer is generally called an inkjet paper, an inkjet-dedicated film glossy paper, a glossy film, or the like. An example of a representative commercial product of the sheet for information transmission having an ink receiving layer is a product name: manufactured by Can〇n Co., Ltd.: Professional (10) Qing, & Photo Paper - Gloss Pro [ Platinum Grade] and gloss G〇ld; Seik〇Ep_ Co., Ltd. trade name: photo paper CHspia (high gloss), photo paper (gloss); Japan Hewlett-Packard Co., Ltd. trade name: Advanced Photo Paper (Gloss); Product name manufactured by FUJIFILM Co., Ltd.: 昼彩 Photo Finishing Pro; Brand name manufactured by Brother Industries, Ltd.: photo gloss paper BP71G, etc. Further, the term "plain paper" refers to paper which is not provided with an ink receiving layer, and there are many commercially available products depending on the use. Among the commercially available plain papers, plain paper for inkjet recording can be exemplified by double-sided plain paper (manufactured by Seik〇Epson Co., Ltd.); PB paper gf_5〇〇 (manufactured by Canon Co., Ltd.); Multipurpose Paper, All-in-one Printing Paper (manufactured by Hewlett Packard). In addition, it is not particularly limited to Plain Paper Copy (ppc) paper, which is also used for inkjet printing, and is also plain paper. The color body of the present invention means that it is colored by any of the following three: 201231566

The ink set of the present invention having the compound and the water-soluble azo compound of the soothing water and the water-soluble azo compound, (b) the water-containing composition, and (c) the compound

The ink composition of the present invention represented by the above formula (1). The material to be colored is the above-mentioned material to be recorded, but the material to be recorded is not colored. The method is preferably, for example, a dip dyeing method, a brushing method, or an ink jet recording method of the present invention. Among the above colored bodies, a color body which is colored by a method is preferable.

Water or a water-soluble organic solvent is excellent in solubility. Moreover, it is also characterized by good filtration for, for example, a membrane filter in the process of producing the ink composition of the present invention. The ink composition of the present invention can impart a yellow record image which is non-sharp, chroma, and high in print density and ideal in hue on a recording material such as plain paper and a sheet for information transfer having an ink receiving layer. image. Therefore, the color image of the photographic style can be faithfully reproduced on the paper, and the ink composition of the present invention does not have solid precipitation, physical property change, hue change, etc. after long-term storage, and the storage stability is extremely good. Even if the ink composition of the present invention is used as an inkjet ink, it is extremely difficult to precipitate a solid due to drying of the ink composition in the vicinity of the nozzle, and the ejector (recording head) is not blocked. Moreover, the ink composition of the present invention is used in a continuous ink jet printer and is used in a relatively long time interval to make the ink owe, or on demand (on_dernan<l-type When the inkjet printer is used intermittently, 'the physical properties will not change. And 31, 2011, 566, an image recorded on a sheet for information transmission having an ink receiving layer by the ink composition of the present invention, in water resistance, moisture resistance, odor resistance, gas resistance, rub resistance, and light resistance For the sake of this, the image quality image is excellent in long-term storage stability. In addition, compared with the conventional inks, color rendering, brightness, and printing density on the paper are excellent, especially in high chroma: it is also excellent. As described above, the water-soluble azo compound of the present invention represented by the above formula (1) and the ink composition of the present invention containing the compound are extremely useful for various ink recording applications and particularly for ink use for inkjet recording. . [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. In addition, in this description, only the special records, "parts" and "% a von quality benchmark, and the reaction temperature 疋 日 内 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The value obtained by absorbing the wavelength is the measured value in the aqueous solution of pH 7 to 8. Further, in each structural formula of the compound Aσ obtained in the examples, the carboxyl group, the sulfo group·# The acidic functional group is in the form of free acid 獾~". In addition, the compound of the present invention obtained in the examples, 1 1ηπ /τ, and the solubility in water in the range of WO g/L or more. [Example 1] (Step 1) 17.7 parts of 5-amino-2-chlorobenzoic acid was adjusted to 32 201231566 with sodium hydroxide, followed by addition of sodium nitrite 7.2 parts for 30 minutes to 5% hydrochloric acid. The diazotization reaction was carried out for 2 hours, and the solution was dissolved in 200 parts of water at pH 6. This solution was stirred at 0 to 10 ° C for 30 parts, and then stirred at 1 ° C for 1 hour to prepare a diazo reaction solution. On the other hand, a part of 2-(sulfopropoxy)aniline was dissolved in 13 parts of water while adjusting to pH 7 with sodium hydroxide, and sodium sulfite and 8.6 parts were used. 35% fumarin, using a general method to obtain a methyl-omega-sulfonic acid derivative, the obtained methyl-sulfonic acid derivative is added to the previously prepared diazo reaction solution, and is at 〇15t, ρΗ2~ Stir under 4 hours for 4 hours. After the reaction liquid was adjusted to pH 以 with sodium hydroxide, the mixture was stirred at 80 to 951 for 5 hours while maintaining the same pH, and further, sodium chloride was added thereto to carry out salting out, and the precipitated solid was separated by filtration. Thus, 10 parts of the azo compound represented by the following formula (9) was obtained in the form of a wet cake.

(Step 2) Add 250 parts of ice water to the trade name of the company: LEOCOLrtmTD90 (surfactant) 〇 1 part and stir vigorously, add 3.6 parts of trimeric gasified cyanide, and then 〇~ 51: Stir for 30 minutes to obtain a suspension. Next, 100 parts of the wet cake of the compound represented by the above formula (9) was dissolved in 2 parts of water, and the suspension was added dropwise to the solution for 3 minutes. After the completion of the dropwise addition, the pH was 6 to 8, 25 to 45. (:Unmix 33 201231566 for 6 hours. Add 1 8.3 parts of 2-aminoethanol to the obtained solution, and stir at pH 7~9, 75~9 (rc for 4 hours). Cool the obtained reaction solution. After 20 to 25 C, 8 parts of propylamine was added to the reaction mixture, and the mixture was stirred for 1 hour at 20 to 25 C. The precipitated solid was separated by filtration, whereby 50.0 parts of a wet cake was obtained. The cake was dried in a hot air dryer of 8 Å «c" to obtain 13.5 parts of a sodium salt (λ max : 383.5 nm) of the water-soluble azo compound of the present invention represented by the following formula (1 〇).

[Example 2] The same procedure as in Example 丄 was carried out except that 24.0 parts of decylamine (40% aqueous solution) was used instead of 18.3 parts of 2-aminoethanol of Example 1 (Step 2). The sodium salt of the water-soluble azo compound of the present invention represented by the formula (11) was 12.5 parts (Amax: 383.0 nm).

[Example 3] The same procedure as in Example 1 was carried out except that the third-stage butylamine 11 〇.0 part was used instead of the 8.3 parts of the aminoethanol of Example 1 (Step 2). The sodium salt of the water-soluble azo nitride 34 (12) 201231566 compound of the present invention represented by the formula (12) is 5.0 parts (λ max : 3 87.0 nm).

[Example 4] The following formula was obtained in the same manner as in Example 1 except that 29.1 parts of 2-furoamine was used instead of 8.3 parts of 2-aminoethanol of Example 1 (Step 2). (丨3) The sodium salt of the water-soluble azo compound of the present invention is 14.0 parts (λ max : 388.5 nm) 〇ho3s(ch2)3o cmQ-n=nhQ-K ho2c Νώ ΗΝ.

(13) [Example 5] The following procedure was carried out in the same manner as in Example 1 except that 40.0 parts of the imine diacetic acid was used instead of the first embodiment (2:1% of the aminoethanol in the step 2). The sodium salt of the water-soluble azo compound of the present invention represented by the formula (14) is 12 〇 (Amax: 399.0 nm).

H02C~H2(/, η2-002Η [Example 6~1 〇·丨35 (14> 201231566 (A) Preparation of Ink According to the above-mentioned Examples 丨 to 5, the even I compound of the present invention [Formula (10) The sodium salt of the formula (14) is used as a coloring matter and mixed in a composition which is not shown in the following Table 4 to prepare a solution, and the ink composition of the present invention is obtained. The obtained ink composition is 〇45, respectively. The pH filter of the μιη filter removes the impurities and prepares the test ink. The pH of the test ink is in the range of 8 〇 to 9.5. Further, in the following Table 4, the "surfactant" is used. The product name SURFYNOLrtm 104PG50 manufactured by Nissin Chemical Co., Ltd. was prepared by using the compounds obtained in Examples 1 to 5 as Examples 6 to 1 respectively. [Table 4] Composition of the ink composition The compound obtained in each example was 3.5 parts of glycerin 5.0 parts... Urea 5.0 parts of mercapto-3-pyrrolidone 4.0 parts - isopropanol 3.0 parts - tetrabutyl alcohol 2.0 parts ~ surfactant 0.1 # ion exchange 77.4 parts of water - a total of 100.0 parts [Comparative Example 1] In the same manner as in Examples 6 to 1 except that the compound described in Example 25 of Patent Document 1 was used instead of the compound of the present invention obtained in each Example, the ink for comparison was prepared. The preparation was carried out as Comparative Example 1. The structural formula of the compound used in Comparative Example 1 is as shown in the following formula (15). 36 201231566

Ϊ〇2η (15) > 2η [Comparative Example 2] In addition to the use of the pigment described in Example 2 of Patent Document 2 in place of the compound of the present invention obtained in each Example, the same as in Examples 6 to 1 In the same way, the ink for comparison is modulated. This ink was prepared as Comparative Example 2. The structural formula of the compound used in Comparative Example 2 is represented by the following formula (16).

[Comparative Example 3J was prepared in the same manner as in Examples 6 to 10 except that the coloring matter described in the Example of Patent Document 4 was used instead of the compound of the present invention obtained in each of the examples. ink. This ink was prepared as Comparative Example 3. The structural formula of the compound used in Comparative Example 3 is represented by the following formula (17).

(B) Mouth ink recording Each of the inks prepared in the foregoing Examples 6 to 10 and each comparative example, 37 201231566, using an ink jet printer (manufactured by Canon Co., Ltd., trade name: PIXUSRTM ip4500), in 5 kinds of gloss The inkjet recording was performed on paper (inkjet paper) as a light resistance test, an ozone gas resistance test, a print density (Dy value) test, and a chroma (C*) test. In the case of inkjet recording, an image pattern ' is produced in such a manner that a reflection density is obtained in several stages of gradation (darkness level) to obtain a recorded matter having a yellow gradation. Each of the obtained samples was used as a test piece to carry out various tests. Glossy Paper 1 : Canon Co., Ltd. Manufactured Product Name: Gloss Pro Platinum Grade ( PT-1 〇 1 ) Glossy Paper 2 : Canon Co., Ltd. Manufactured Product Name: Gloss Gold ( GL-101 ) Glossy Paper 3 : Seiko Epson Limited Share Company name: Photo Paper Crispia (High Gloss) Glossy Paper 4: Hewlett-Packard Co., Ltd. Manufactured by Advanced Photo Paper (Q8861A). Glossy Paper 5: Manufactured by Brother Co., Ltd., trade name: Photo Paper (BP71GA4). In the light resistance test and the ozone gas resistance test, the reflection density was measured for the portion of the recorded matter before the test in which the reflection density D value was closest to 1 。. The chroma (C* value) and the reflection concentration (1) 丫 value are the places where the depth of the gradient is the highest. The chroma and the reflection density were measured using a color measurement system (trade name: SpectroEyeRTM, manufactured by X-rite Co., Ltd.). Color measurement 进行 was carried out under the conditions of a concentration standard of DIN (Deutsche Industrie Nomung Colour System), a viewing angle of 2 degrees, and a light source of D65. 38 201231566 The various test methods for redundant images and the evaluation methods for test results are recorded below. (c) Light resistance test of fox lamp. Each test piece was placed on a stand and a xenon arc lamp weathering tester XL75 [manufactured by Suga Test Machine Co., Ltd.] was used at a temperature of 24 ° C, humidity of 60/6 RH, and 0.36 W. Irradiation hours under the condition of illuminance of /m2. The color measurement system was used to measure the reflection density of each test piece after the test, and the color residue was calculated by (reflection concentration after the test/reflection concentration before the test) χ1〇〇 (%). The results, the results of Examples ό to 10 and Comparative Examples 1 to 3 all showed good results. (D) Ozone gas resistance test using Ozone Weather Meter OMS-H [manufactured by Suga Test Machine Co., Ltd.] Each test piece was subjected to an ozone gas concentration of 1 〇 ppm, a humidity of 6 〇 % RH, and a temperature of 24 ° C. Place it for 24 hours. The reflection density of each test piece after the test was measured by the color measurement system, and the residual ratio of the dye was calculated by (reflection concentration after the test/reflection concentration before the test) X100 (%), and the result was determined. Examples 6 to 10 and Comparative Examples 丨 to 3 all showed good results. (E) Print density test The yellow reflection density (Dy value) was measured by the colorimetric system described above for the gradient portion having the highest reflection concentration in each test piece. The results are shown in Table 5 below. 39 201231566 [Table 5] Reflection density glossy paper 1 Gloss paper 2 Gloss paper 3 Gloss paper 4 Gloss paper 5 Example 6 2.09 2.11 2.22 2.02 2.21 Example 7 2.12 217 2.24 2.04 2.23 Example 8 2.09 2.19 2.29 2.06 2.25 Example 9 2.08 2.15 2.27 2.04 2.23 Example 10 2.03 2.13 2.22 1.95 2.19 Comparative Example 1 1.57 1.78 1.86 1.75 1.92 Comparative Example 2 1.79 1.90 2.04 1.83 2.05 Comparative Example 3 1.91 1.93 2.06 1.82 1.96 From the results of Table 5, the above yellow print density ( Among the Dy values, Comparative Example 1 showed extremely inferior results to Examples 6 to 10 in any of the glossy papers, and Comparative Examples 2 and 3 showed inferior results to Examples 6 to 10. . (F) Saturation test The yellow chroma (C* value) was measured by the above colorimetric system for the gradation portion having the highest reflection concentration in each test piece. The results are shown in Table 6 below. [Table 6] Chroma (C*) Glossy Paper 1 Glossy Paper 2 Glossy Paper 3 Glossy Paper 4 Glossy Paper 5 Example 6 115 110 116 110 114 Example 7 115 112 116 110 114 Example 8 113 111 116 109 114 Implementation Example 9 112 110 115 108 113 Example 1 0 112 109 115 106 111 Comparative Example 1 93 96 99 97 101 Comparative Example 2 100 97 105 96 103 Comparative Example 3 106 106 112 103 108 40 201231566 It is known from the results of Table 6 In the degree (C* value), 'Comparative Example 1' showed extremely inferior results to Examples 6 to 1 in any of the glossy papers. Moreover, Comparative Example 2 showed results inferior to Examples 6 to 1〇. According to the results of Tables 5 and 6, the comparative examples showed extremely inferior results to the respective examples in terms of yellow print density (Dy value) and chroma (C* value) in any of the glossy papers, and In Comparative Example 2, in terms of yellow print density (Dy value) and chroma (C* value), the results of the respective examples were inferior in any of the glossy papers. In Comparative Example 3, although the chroma (C* value) is relatively good in glossy papers 2, 3, and 5, it is glossy paper! And 4 is inferior to the respective examples, and in terms of the yellow printing density (value), the results of the respective examples are inferior to those of the respective examples. On the other hand, in each of the examples, excellent results were obtained in all glossy papers in terms of chroma (c* value) and yellow print density (Dy value) of the recorded matter. Therefore, it can be known that the water-soluble azo compound #, and contains. The ink composition of the present invention of the present invention has a high-definition hue in many types of glossy paper, and has a high yellow print density value, and the color is also different from the type of glossy paper. Irrelevant and quite excellent. [Industrial Applicability] = A water-soluble azo compound of Ming, that is, a yellow pigment, and a yellow ink composition of the present invention containing a high color; can provide a high color rendering and a recorded image. Therefore, the compound and the ink containing the compound 41 201231566 are very useful for various recording applications, and particularly for inkjet recording applications. [Simple diagram description] None [Main component symbol description] None 42

Claims (1)

201231566 VII. Patent application scope: 6 2. 溶 Soluble occlusive compound * A water-soluble azo compound or a salt thereof, which is represented by the following formula (1): Wherein 'X represents an integer from 2 to 4', the base A represents the amine group as shown in the lower one, /H - N (2) X(CH2)w-OH, and 'W represents 2 in the formula (2) Integer to 6), -<Η Ο) In the formula '(CH2)v-CH3, V denotes an integer from 〇 to 3), η3〆\ιη3, H2—^p /CH2—^co2h, η2co2h (4) (5) (6) Ο) (2) The water-soluble azo compound described in the above item (i) of the patent application, wherein 乂 in the above formula (1) is 3. The water-soluble azo compound or the salt thereof as described in the above formula (1), wherein the azo azo compound is as follows. Equation (7): ~ (7) An ink composition comprising the water-soluble azo compound or a salt thereof according to any one of the above items. 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 used for ink jet recording. An ink jet recording method which uses the ink composition as described in claim 4 as an ink, and causes the ink droplets of the ink to be ejected on the recording material according to the recording signal to be recorded. 8. The ink jet recording method according to claim 7, wherein the recorded material is a sheet for information transfer. 201231566 9' The above-mentioned information transfer sheet as described in item 8 of the patent application scope is a method of recording 5, wherein, β, 疋 通, or B and female material, the ink receiving layer + # _ The sheet layer 3 of the ink receiving layer has a porous white inorganic substance. Ϊ́θ. A coloring body which is formed by (a) such as 申谙真夭丨丨^^#; a salt-soluble azo compound as described in item 1 or a second thereof) :: "Ink composition of the water-soluble azo compound cooker salt described in item 1 of the benefit range; and (including a water-soluble azo compound / salt, as described in the scope of the patent application) An ink composition of a water-soluble organic solvent. A seed color body which is colored by an ink jet recording method as described in Patent Application No. 7. Spray 2· An ink jet printer loaded with a container containing the ink composition as described in claim 4 of the patent application. 45 201231566 IV. Designation of representative drawings: (1) The representative figure of the case is: No. (2) A brief description of the component symbols of the representative figure: No. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0