TW200948904A - Hydrosoluble anthrapyridone compound and salt thereof, ink composition and colored article - Google Patents

Abstract

The present invention relates to a novel anthrapyridone compound represented by the following formula (1) (provided that R1 represents alkyl group and the like; R2 represents hydroxyl group, substituted or unsubstituted aniline group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted mono- or di-alkylamino group and the like; and R3 and R4 independently respectively represents hydrogen atom, halogen atom, carboxyl group and the like.) and a salt thereof. The present invention provides a magenta pigment having a hue with high sharpness which is appropriate for ink-jet recording, having a high fastness with respect to recorded article, particularly having a high water-resistance of image recorded on common papers, and having an excellent preservation stableness, and an ink composition containing the same.

Description

200948904 考六, invention description: [Technical field of invention] There is such a water-soluble onion and residual compound" Go Li Yue people =: Γ成物, and this color Zhao, contained in various color recording methods, The method of brush recording, that is, the sneezing, one of the methods of inkjet printing. These methods are all carried out in, for example, paper, film, cotton, and the like. Since the attachment heads are not in direct contact with the material to be recorded, the sputum method is easy to be miniaturized, high-speed, and suffocating. It is expected that there will be = point, so it grows as a pen and a felt pen (fel1:). In the past, it has been used as an ink for ink-based inks and inks for inkjet recording. In these aqueous inks, ink is blocked by a water-soluble dye which is a pigment, and water-soluble is added. The printing ink of the ink jet nozzle is required to be able to impart sufficient concentration:: unequal to the plug, the dryness of the recorded material is excellent, etc. Further, for the shape 4, the wood is less stored f U The resulting recorded image requires water resistance, moisture resistance, resistance to resistance, and resistance to gas _ various fastness. The nozzle clogging of inkjet is mostly due to the knife-specific chelating agent or additive in the ink near the nozzle. When it is evaporated, it becomes a state in which the amount of water is small and the amount of the solvent or the additive is large, and the dye is crystallized and precipitated. Therefore, even if the ink is dried by the dry matter, it is difficult to crystallize and precipitate, and it becomes a 4321100 200948904 *. Non-critical performance requirements. For this reason, "there is a problem with solvents or additives." It is also one of the properties required for pigments. However, when images or text information on a color display of a computer are recorded in color by an inkjet printer, yellow (7), magenta (M), cyan M (c), and black (1) are generally used. The 4-color ink is subjected to subtractive color mixing, whereby the recorded image is presented in color. If the image of the addition of red (8), green (6), and blue (8) in a CRT (Braun: Braun: Wide) display or the like is to be faithfully reproduced in a subtractive mixed color image, then It is desirable that the respective pigments used in the ink, in particular, the respective pigments of Y, M, and C have a hue close to the standard and are vivid. Further, the ink is required to have long-term storage stability, and the density of the printed image as described above is high, and the fastness of the printed image is excellent. In recent years, due to the development of inkjet printing technology, the printing speed has been significantly improved, and similar to the laser printing using electronic toner, there is an inkjet printer used for plain paper which is mainly used in the office environment. The trend of document printing. Inkjet printers have the advantage of not needing to choose the type of recording paper, and the mechanical price is relatively cheap, especially in small and medium-sized environments such as studio workers (s〇h〇). When an ink jet printer is used for printing on plain paper, the hue and water resistance tend to be emphasized in various qualities required for printing. In order to satisfy these properties, particularly water resistance, a method of using a pigment ink is proposed. However, a pigment is used as a pigment ink, which is different from a dye ink, and is likely to be a solution but a dispersion. As a result, the problem of poor stability is preserved, or there is a problem of blocking the nozzle of the printer's recording head. Also, when using the pigment printing 321100 200948904 ink, there are many problems with the rubbing resistance, and the color is also inferior to the dye. On the other hand, it is generally considered that when a dye ink is used, the problem of using such a pigment ink is less likely to occur. However, it is apparent that dye inks are inferior to pigment inks, especially in terms of water resistance, and it is highly desirable to improve them. Since ancient times, there have been many proposals for improving the water resistance of dyes on plain paper. As the inkjet magenta pigment which is excellent in water resistance and has improved hue, water resistance and the like, for example, the indoloquinone ketone-based magenta disclosed in Patent Documents 1 to 11 is known. For example, Patent Document 1 discloses a magenta pigment which is excellent in water and/or moisture, but its water resistance, particularly the water resistance of a recorded image when recorded on plain paper, cannot be said to sufficiently satisfy the market. Claim. Therefore, it is required to have the same excellent water resistance on a wider variety of plain papers, and further to a magenta pigment which is excellent in light, hue, or color density. [Patent Document 1] JP-A-2000-109464 [Patent Document 2] [Patent Document 3] [Patent Document 4] [Patent Document 5] [Patent Document 6] [Patent Document 7] [Patent Document 8] [Patent Japanese Unexamined Patent Application Publication No. JP-A No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No [Patent Document 10] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-188. Problem to be Solved The object of the present invention is to provide an ink composition which is excellent in preservation stability of water-soluble magenta cord and T 帙 pigment, and which has high solubility in water and is suitable for ink jetting. Recording J phase two pairs of odor, high color density, and the light fastness of the recorded matter, the financial auditory (trees such as oxygen gas), moisture resistance, and especially the excellent fastness recorded in the ordinary paper department . (Means for Solving the Problem) In order to solve the problem of the prior art, the present inventors have found out that the water-soluble chlorpyrifos which is represented by the following formula (1) and the pigment thereof are found by the results of concentration. The ink-receiving grade can solve the above-mentioned problems, and the cost is 70%. That is, the present invention relates to the following: ❾(1) The enthalpy shown in the following formula (1). A pyridine ketone compound or a salt thereof:

Mono-carboylalkyl, or cyano lower base 7 321100 200948904 R2 represents a hydroxyl group; an alkoxy group; an amine group; a halogen atom; having a group selected from the group consisting of a -sulfonic acid group, a carboxyl group, an alkoxy group, an amine group An anilino group having at least one group as a substituent in the group of a mercapto group, a cyano group, an alkyl group, an anthranyl group, a phenoxy group, an amine group, a hydroxyl group, and a hydrogenthio group; an unsubstituted anilino group; An aralkylamino group having at least one group selected from the group consisting of an acid group, a carboxyl group, an alkoxy group, an oxo group, an amino group, a cyano group, and a hydroxyl group as a substituent; An unsubstituted aralkylamino group; having an amine group selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group, a ketone group, an amine fluorenyl group, a gas group, an anilino group, a phenoxy group, a thiol C1 to C4 alkyl group a mono- or dialkylamino group having at least one group of an alkylamino group, an amine group, a hydroxyl group, and a hydrogenthio group as a substituent; an unsubstituted mono or dialkyl group; The amino group, R3 and R4 each independently represent a hydrogen atom; a halogen atom; a thiol group; a oxycarbonyl group; an acid group; a hydroxyl group; a substituted or unsubstituted C1 to C12 alkyl group; Substituted or unsubstituted aminomethyl fluorenyl; substituted or unsubstituted amine sulfonyl; substituted or unsubstituted amine; nitro; C1 to C12 alkyl; or C1 to C4 alkoxy) . (2) A ketone ketone compound or a salt thereof, wherein (2) is a hydroxyl group; an alkoxy group; an amine group; and has a group selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group, and an amine group. An anilino group having a substituent in the group of a mercapto group, a cyano group, an alkyl group, an anilino group, a phenoxy group, an amine group, a hydroxyl group, and a hydrogenthio group; an unsubstituted anilino group; having a sulfonic acid selected from the group consisting of An arylalkylamine group having a substituent in the group of a group, a carboxyl group, an alkoxy group, a ketone group, an amino group, a cyano group, and a hydroxy group; an unsubstituted arylalkylamine 8 321100 200948904 * a base selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group, a ketone group, an aminomethyl fluorenyl group, a cyano group, an anilino group, a phenoxy group, a carboxy C1 to C4 alkylamino group, a di(C1 to C4) alkane a mono- or dialkylamino group as a substituent in the group of an amino group, an amine group, a hydroxyl group, and a hydrogenthio group; or an unsubstituted mono- or dialkylamino group. (3) The acridinone compound or a salt thereof according to (1) or (2), wherein R is a hydrogen atom or a methyl group. (4) The hydrazide compound or a salt thereof according to (1) or (2), wherein R + represents a hydrogen atom or a fluorenyl group, and either one of R 3 or R 4 is a carboxyl group; an alkoxycarbonyl group; Or unsubstituted amino fluorenyl group, the other being a hydrogen atom; a halogen atom; a carboxyl group; an alkoxycarbonyl group; a sulfonic acid group; a hydroxyl group; a substituted or unsubstituted C1 to C12 alkyl group; a substituted or unsubstituted amino group Mercapto; substituted or unsubstituted amine sulfonyl; substituted or unsubstituted amine; nitro; C1 to C12 alkyl sulfonyl; or C1 to C4 alkoxy. (5) The indolopyridone compound or a salt thereof according to any one of (1) to (4), which is represented by the following formula (2):

(wherein Rs I?3 and R4 represent the same meanings as R2, R3 321100 200948904 and 匕 in the above (1) to (4)). (6) The oxime ketone compound or a salt thereof according to any one of (1) to (5), wherein either one of L or R4 is a carboxyl group; an alkoxycarbonyl group; or a substituted or unsubstituted amine a fluorenyl group, the other being a hydrogen atom; a halogen atom; a carboxyl group, an alkoxy group; a carboxylic acid group; a transradical; a substituted or unsubstituted C1 to C12 alkyl group; a substituted or unsubstituted aminomethyl fluorenyl group Substituted or unsubstituted amine fluorenyl; substituted or unsubstituted amino group; 5 octyl; C1 to C12 alkyl group; or C1 to C4 alkoxy group. (1) The anthrapyridone compound or a salt thereof according to any one of (1) to (6) wherein R2 is a trans group; an amine group; an anilino group substituted with a carboxyl group; an unsubstituted anilino group; a substituted aralkylamino group; having an amine selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group, a ketone group, an aminomethyl fluorenyl group, a cyano group, an anilino group, a phenoxy group, a carboxy C1 to C4 alkyl group, an amine a monoalkylamine group in which at least one group of the group, the hydroxyl group, and the hydrogenthio group is substituted as a substituent; or an unsubstituted monoalkylamine group. (8) The indolopyridinone compound or a salt thereof according to any one of (1) to (5), wherein 'R2 is a trans group; an amine group; an anilino group substituted with a carboxyl group; an unsubstituted anilino group; a partially substituted carboxy group of a C1 to C4 alkyl group; a mono C1 to C12 alkyl group substituted with a buffer; or an unsubstituted monoalkylamino group, either one of R3 and R4 is a carboxyl group, or none The substituted aminomethylmercapto group and the other one are a hydrogen atom, a halogen atom or a carboxyl group. (9) The anthrapyridone compound or a salt thereof according to any one of (1) to (5), wherein 10 321100 200948904 • r 2 is a hydroxyl group; an amine group; an anilino group substituted with a carboxyl group; an unsubstituted J aniline a phenyl group to a C4 alkylamine group substituted with a carboxyl group; a mono C5 to C11 alkylamino group substituted with a carboxyl group; or an unsubstituted C5 to C11 monoalkylamino group, R3 or R4 One is a treason; the other is a hydrogen atom or a halogen atom. (10) The indolo acridone compound or a salt thereof according to any one of 0) to (5) wherein R2 is a hydroxyl group; an unsubstituted anilino group; a phenyl group substituted with a carboxyl group in a C1 to C4 alkane a monoamine group; or a mono C5^ to C11 alkylamino group substituted by a carboxyl group; one of R3 and R4 is a tracing group, and the other is a hydrogen atom or a halogen atom. (11) An ink composition comprising the indole acridine compound of any one of the above (1) to (10) or a salt thereof as a coloring matter, and further comprising water. (12) The ink composition of (11), which contains a water-soluble organic solvent. (13) An ink composition for inkjet recording, comprising the anthrapyridone compound of any one of (1) to (10) or a salt thereof as a pigment, and the retanning water and water-soluble organic Solvent. (14) The ink composition according to any one of (1) to (13), wherein the total of the indenacridone compounds of any one of the above (1) to (10) is contained as a pigment In the mass, the content of the inorganic impurities is 1% by mass or less. The range of 0.1 to 20% by mass of the content of the anthrapyridone compound is 0.1 to 20% by mass, based on the total mass of the ink composition. . (16) An ink jet recording method by which the ink composition containing the oxime D or the ketone compound of any one of the above (1) to (10) or a salt thereof is 11 11100100 200948904 In response to the recording signal being ejected and attached to the inkjet recording method of (17), such as (16), the heart, and the order 5 have been recorded. Use a thin sheet. ', broke 5 own materials for information transmission (18) such as (17) inkjet recording method, Α by _ _ color: machine = general information transmission sheet. The soil is similar to the material (10) - the coloring body '" contains the above (1) to (10) towel - ❹ the side composition or its salt and the ink composition of both water or water and water-soluble money-opening solvent is colored. (10) The color body of (10), wherein the coloring is printed by the ink of the mouth. (9) - The ink jet printer is filled with the compound (4) or a salt thereof containing the above-mentioned items (1) to (10) A container containing an ink composition of water and a water-soluble organic solvent. (22) A pyridone compound of the formula (1) or a salt thereof, wherein L is a methyl group, (23) is a '' and a κ 如 as in (22) A compound or a salt thereof, wherein one of the compounds is a silk or a halogen atom. (Effect of the invention) The water-soluble indenofluorene compound of the above formula (1) of the present invention or a salt thereof has a magenta color The pigment, the ink composition containing the pigment, is applicable to various inks, and is particularly suitable for use as an ink for inkjet recording of magenta. The compound or a salt thereof is excellent in solubility in water or a water-soluble organic solvent. In terms of the advantages in the process of manufacturing the ink composition, there is an example of 321100 12 2009 48904 : : : : : : : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The bright and high-brightness composition is in the long-term door: 2: There is no crystal precipitation, crystallization, etc. after storage of the ink 4 of the present invention having the compound as a pigment, and the storage stability is extremely steep, and the hue change composition is used as the mouth. = using the ink, paper, etc. of the present invention; that is, when the ink is used, it is not necessary to select the recorded material (for example, it is also possible to apply a printed matter having a suitable magenta hue. Re-image. " The color comparison of the photo grades faithfully reproduced on the paper: the composition of the ink of the Ming Dynasty is recorded in the same way as the dye ink of the past. The water is extremely improved. Moreover, the thinner such as the thinner is used: ί κ or photo When inkjet is used for image quality, the ink is applied to the surface of the recorded material to resist the ozone resistance of the material, such as water resistance, moisture resistance, and time-lapse. Sex is good, photo grade is not It is suitable for the ink to be described as a brush. Thus, the above-mentioned training is used as a feature for inkjet inks, particularly for inkjet inks: a mouthpiece [Embodiment j 117] The present invention will be described in detail. In addition, in the investigation of the sulfonic acid group and the carboxyl group, etc., the acidity is particularly limited, and the window η of the invention does not show the form of the free acid. Also, the J (the) product of the product or the material of the material is changed to magenta = 32Π〇 〇13 200948904 Ink for ink cartridges or pigments for magenta inks. Hereinafter, for convenience of explanation, the present invention includes "the indole pyridone compound of the present invention or a salt thereof" and is simply "the indole pyridine of the present invention". The "keto compound", the "compound of the formula (1)", the "compound of the formula (2)", and the "compound of the present invention" are also used in the same manner as in the case of including each salt. The indolopyridone compound of the present invention is represented by the above formula (1) or / and formula (2), wherein in the formula (1), R! represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a mono or Dialkylaminoalkyl, or cyano lower alkyl.

The carbon number of the alkyl group in Ri is usually C1 to C10, and preferably C1 to C6' is preferably C1 to C4, more preferably C1 to C3. The alkyl group may, for example, be a linear or branched alkyl group, and is preferably a straight chain. Preferred examples thereof include a linear C1 to C6 alkyl group such as a mercapto group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, and a n-hexyl group; an isopropyl group, an isobutyl group, and a second group; A branched chain C1 to C6 alkyl group such as a benzyl group, a tributyl group, an isopentyl group, a 2-methylbutyl group, a third pentyl group, and an isohexyl group. As the hydroxy lower alkyl group in Ri, 'usually a hydroxyl group C1 to alkyl group' is preferably a base group C1 to C6, preferably a base group ci to C4, and the alkyl moiety is preferably a straight chain. . Specific examples thereof include a benzyl group, a light propyl group, and a butyl group. As the mono or dialkylaminoalkyl group in L, it is usually a mono or di(C1 to C8)alkylamino group (Cl to C8) alkyl group. It is preferably a mono- or di-(C1 to C6) alkylamino (C1 to C6) alkyl group, preferably a mono or di(π to C4)alkylamino group (C1 to C4) alkyl group. The alkyl moiety may be either a linear or branched chain of 321100 14 200948904, but is preferably a linear one. Specific examples of the monoalkylamino group include, for example, a mercaptoaminopropyl group and an ethylaminopropyl group. Specific examples of the dialkylaminoalkyl group include dimethylaminopropyl group and diethylaminoethyl group. As the cyano lower alkyl group in R1, it is usually a cyano C1 to C8 alkyl group, and a cyano C1 to C6 alkyl group is preferred, and a cyano C1 to C4 alkyl group is more preferred. The alkyl moiety may be Straight chain or branching is preferred, and linear is preferred. Specific examples thereof include cyanoethyl, cyanopropyl, cyanobutyl, decyl cyanopentyl, cyanohexyl, cyanoheptyl, and cyanooctyl. As a preferred R!, for example, a hydrogen atom or a C1 to C4 alkyl group is preferred, and a hydrogen atom and a methyl group are preferred, and a mercapto group is particularly preferred. When Ri is a methyl group, the above formula (1) is represented by the above formula (2). In the above formula (1) or (2), R2 represents a hydroxyl group; an alkoxy group; an amine group; a halogen atom; and has a group selected from a sulfonic acid group, a carboxyl group, an alkoxy group, an aminomethyl fluorenyl group, a cyano group, an alkyl group, An anilino group, a phenoxy group, an amine group, a hydroxyl group, and a thiol group (if not particularly limited, it means an unsubstituted thiol group or a substituted thiol group such as a C1 to C4 alkylthioindole group, Further, the C1 to C4 alkylthio group is preferably the same as the anilino group having at least one group as a substituent; or the unsubstituted anilino group; having a selected from the group consisting of a sulfonic acid group, a sulfhydryl group, and a pyridyl group. a arylalkylamine group having a gas group, a ketone group, an aminocarbamyl group, a cyano group, and at least one group in the group of a group as a substituent; or an unsubstituted aralkylamino group; Acid group, buffer group, alkoxy group, Benyl group, aminomethylmercapto group, cyano group, anilino group, phenoxy group, trans-C1 to C4-based amine group, di(ci-C4)alkylamino group, An amine group, a hydroxyl group, and a hydrogenthio group (if not particularly limited, it means an unsubstituted thiol group or a C1 to C4 alkyl thiol group substituted 321100 15 200948904 hydrogen: ^ meaning ' Further, it is preferably a C1 to C4 alkylthio group, the same as the above: a mono- or di-decylamino group having at least one substituent as a substituent; or an unsubstituted mono- or monoalkylamino group. When the amount of carbon in the group R2 (including when it has a substituent), the carbon number of the base is usually C1 to C6, and the oxyalkyl group of ci to c4 is preferred. The alkyl group may be a linear or branched chain, but a linear one is preferred. Specific examples of the alkoxy group include a methoxy group such as a methoxy group, an ethoxy group, a propylene group, a n-butoxy group, a n-pentyloxy group, and a n-hexyloxy group; The alkoxy group of the branched chain G1AG6 such as propoxy 'isobutoxy' tert-butoxy, isodecyloxy and isohexyloxy. Field R2 is an anilino group selected from the group consisting of an acid group, a county, an alkoxy group (having a C1 to C4 alkoxy group as a Ji), an aminomethyl sulfonyl group, a cyano group, and a hospital base (with a ci to (tetra) fluorenyl group). When an epoxy group, an amine group, a thiol group, and a gas-sulfur group (p. a straight C4 alkylthio group) are used as a substituent of an anilino group (substituted anilino group), The number of the substituents is usually i to 4' and preferably 1 to 3, preferably 1 or 2. More preferably, the specific example of the substituted anilino group is exemplified by An anilino group substituted with a repeating acid group such as a 3-, an acid anilide group, a 4-acid anilide group, an & benzoic acid anilide group; a 2-stage anilino group, a 3-hydroxy anilide group, An anilino group substituted with an anthracene such as an anthranyl group substituted with an aniloid group such as a 4-aminoamino group and a 3, bis-diphenylanilide group, or a 4-methoxyanilino group (replaced by ci to c to find an oxy group) An anilino group is preferred; an anilino group substituted with an amino group such as an aminomethylmercaptoanilide group or a 3-aminomethylmercaptoanilide group; Erjing 32J100 16 200948904 . Alkyl substituted anilino (preferably, an anilino group substituted with a C1 to a C6 alkyl group), an anilino group substituted with an anilino group and an acid group, such as a 4-amino-3-acid as a basic amino group; 4-phenoxyanilinyl group An anilino group substituted with a phenoxy group; an anilino group substituted with an amine group such as a 4-aminoanilino group; an anilino group substituted with a hydroxyl group such as a 2-hydroxyanilino group and a 3-hydroxyanilino group; and a 4-methyl group An anilino group substituted with a thiol group of a C1 to C4 group; As the aniline group in R2, an anilinyl group substituted with a sulfonic acid group, an anilino group substituted with a carboxyl group, or an unsubstituted anilino group is preferred, and an amino group substituted with a carboxyl group or an unsubstituted anilino group is preferred. Preferably, the unsubstituted anilino group is more preferred. When R 2 is at least one selected from the group consisting of a carboxylic acid group, a slow group, an anthracene group (preferably from Ci to C 4 alkoxy group), a ketone group, an aminocarbamyl group, a cyano group, and a hydroxyl group. When the group is a substituent group, the number of substituents is usually 1 to 4', and preferably 1 to 3, preferably 1 or 2. More preferably, it is 1. The aryl moiety of the substituted arylamino group or the unsubstituted arylamino group in R2 is usually an aromatic group of an early ring or a condensed ring of C6 to C10, and specific examples thereof include a phenyl group or Naphthyl. The aryl moiety is preferably a phenyl group. Further, the carbon number of the alkyl group of the arylamino group is usually from Ci to 匸6, preferably from C1 to C4, more preferably from C1 to C3. The alkyl group may be either a straight chain or a branched chain, but is preferably a linear chain. The aralkylamino group is particularly preferably a substituted or unsubstituted phenyl C1 to C4 alkylamino group. The above substituent may be substituted at any part of the aryl moiety or the alkyl moiety of the aralkylamino group, but is preferably substituted in the alkyl moiety. 321100 17 200948904 The aralkylamino group may, for example, be an aralkylamino group substituted with a sulfonic acid group, an arylalkylamino group substituted with a thiol group, an arylalkylamino group substituted with a carboxyl group, or an alkoxy group. A substituted aralkylamino group (preferably an aralkylamino group substituted by a C1 to C4 alkoxy group), an arylalkylamine group substituted by a ketone group, or the like. More specifically, for example, those having a substituent in the aryl moiety may, for example, be a 4-sulfonic acidbenzylamino group, a 3-methoxybenzylamino group, a 4-cyanobenzylamino group or a 4-hydroxy group. A phenethylamino group or the like has a sulfonic acid group on an aryl group, an alkoxy group (preferably a C1 to C4 alkoxy group), a cyano group or a hydroxyalkyl group of a hydroxyl group, and the like, and has a substituent at the alkyl moiety. For example, 2-phenyl-1-carboxyethylamino group, 2-phenyl-2 ketoethylamino group, 2-phenyl-1-aminoformamidoethylamine group, etc. The aryl group having a benzyl group, a keto group or an aminomethyl fluorenyl group, and an unsubstituted arylalkyl group may, for example, be a benzylamino group, a 2-phenylethylamino group or a styrene-acrylic group. An unsubstituted aralkylamino group such as an amino group or a 1-phenylethylamino group. Further, the arylalkylamine group in which the alkyl group is a branched chain may, for example, be a 2-phenylisopropylamino group or the like. The aralkylamino group is preferably a carboxy-substituted aralkylamino group, preferably substituted by a carboxyl group at the carboxyl group-substituted aralkylamino group of the alkyl moiety, and substituted with a carboxyl group at the alkyl moiety. More preferably, a C1 to C4 alkylamine group. When R 2 is selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group (preferably a C1 to a alkoxy group), a ketone group, an aminomethyl fluorenyl group, a cyano group, an anilino group, a phenoxy group, and a thiol group As a group of at least one group of a C4 alkylamino group, a di(C1 to C4) alkylamino group, an amine group, a trans group, and a thiol group (preferably a C1 to C4 alkylthio group) a substituent of a mono or dialkylamino group (hereinafter, referred to as a substituted mono or dialkylamino group, or an unsubstituted mono or dialkylamino group 18 321100 200948904 . The alkyl moiety of the unsubstituted mono or dialkylamino group is usually C1 to C12' and preferably C5 to C12, more preferably C5 to C11. Further, when it is a substituted or unsubstituted-alkylamino group, the alkyl moiety is preferably about C1 to C8 depending on the case. The alkyl group may be either a straight bond, a branched chain or a ring, but a straight chain or a branched chain is preferred, and a straight chain is preferred. As the early or dialkylamino group, the monoalkylamine group is preferred, whether substituted or unsubstituted.个 the number of substituents in the substituted mono or dialkylamino group is not limited to 'generally 1 to 4, preferably 1 to 3, preferably 1 or 2, more preferably such a group. The substituent may be substituted on any of the carbon atoms of the alkyl group in the C1 to C12 alkylamine group, but it is preferably substituted with at least one substituent at the terminal carbon atom. Specific examples of the mono- or dialkylamino group include, for example, an alkylamino group substituted with a sulfonic acid group such as a 2-sulfonic acid ethylamino group; a carboxymethylamino group, a fluorenylethylamine Base, 2-sulfoethylamino, 1,2-dicarboxyethylamino, hydrazine, 3-formed dicarboxypropylamino, 3-carboxypropylamino, 4-carboxybutylamino, 5 —carboxypentylamino, 6-carboxyhexylamino, 7-carboxyheptylamino, 8-monocarboxyoctylamino, 9-carboxydecylamino, 10-carboxydecylamino, carboxyundecyl a linear mono- or dialkylamino group, such as an alkylamino group, and a 12-carboxydodecylamino group, and a bis(monomethyl)amino group, which is substituted with a buffer group, a carboxy-substituted branched alkylalkyl group such as 2-dimethylethylamino group and carboxy- 3,3-dimethylpropylamino group; 2-carboxy-cyclopentylamino group and the like substituted by a carboxyl group a cyclic alkylamino group; an alkyloxy group substituted by an alkoxy group such as a 3-ethoxypropylamino group (a mono or dialkyl group substituted by a C1 to C4 alkoxy group) is a monomeric group of 32100 19 200948904 a keto group-substituted alkylamine group; 3-ketobutylamino group; Alkylmethylamino group substituted by aminomethyl fluorenyl group; alkylamino group substituted by cyano group such as 3-cyano, propylamino group; 2-phenylaminoethylamino group An alkylamino group substituted with an anilino group; an alkylamino group substituted with a phenoxy group such as a 2-phenoxyethylamine group; a hydroxyl group such as an N-(3-hydroxypropyl)aminoethylamino group An alkylamino group substituted with a C1 to C4 alkyl group; an alkylamino group substituted with a di(C1 to C4)alkylamino group such as diethylaminoethylamine; an amino group such as an aminoethyl group Substituted alkylamino group; 2-hydroxyethylamino group and bis(2-hydroxyethyl)amino group and the like mono or di(hydroxy substituted alkyl) amine group; 2-decylthioethyl hydrazine An alkylamino group substituted by a C1 to C4 alkylthio group (or a C1 to C4 alkylthiol group); a mercaptoamine group, an ethylamino group, a propylamino group, a butylamino group, a pentylamine group Base, hexylamino, heptylamino, octylamino, decylamino, decylamino, undecylamino and decylamino, and dinonylamino, Unsubstituted single or two such as ethylamino, dipropylamino and dibutylamine Alkyl amine; and 2-ethylhexyl group, etc. The unsubstituted branched chain alkyl group; cyclohexyl group, etc. The unsubstituted cyclic alkyl group; and the like. ◎ As a suitable monoalkylamine group, for example, a mono C1 to C12 alkylamino group substituted with a sulfonic acid group, a mono ci to C12 alkylamino group substituted with a carboxyl group, or an unsubstituted single C1 to a C12 alkylamino group, preferably an early C1 to C12 alkylamino group substituted by a carboxyl group, or an unsubstituted mono ci to C12 dlay amine group, more preferably a mono C1 to C12 alkylamine substituted by a carboxyl group The base is particularly preferably a mono C5 to C11 alkylamino group substituted with a carboxyl group. The sulfonic acid group or carboxyl group in these groups may be substituted on any of the carbon atoms of the alkyl group in the C1 to C12 alkylamino group, but it is usually preferred to substitute a carbon atom at the terminal. 20 321100 200948904. As a suitable dialkylamino group, for example, an unsubstituted dibasic amine group (preferably a C1 to C8 compound amine group) and a double (suppressed base group) are exemplified. Amino group (preferably substituted with bis (C1 to C8) amine group), 2 bis (hydroxy substituted hydroxy group) amine group (with bis (hydroxy substituted α to (7) amide) amine group Better). In the case of (4), in R2, for example, a fluorine atom, a gas atom, a bromine atom or the like is preferably a gas atom or a desert atom, and a chlorine atom is more preferable. In the above formula (1) or formula (2), R3 and each independently represent a hydrogen atom; a halogen atom; a carboxyl group; an alkoxycarbonyl group; a sulfonic acid group; a hydroxyl group; a substituted or unsubstituted C1 to C12 alkyl group; Amine fluorenyl; substituted or unsubstituted amine sulfonyl; substituted or unsubstituted amine; nitro; ci to C12 alkyl fluorenyl; or Cl to C4 alkoxy. Examples of the functional atom in R3 and R4 include a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is preferred. As the alkoxycarbonyl group in R3 and R4, usually a C1 to C6 alkoxycarbonylcarbonyl group is preferred from a C1 to C4 alkoxycarbonyl group, and a C1 to C3 alkoxycarbonyl group is more preferred. The alkoxy moiety of the alkoxycarbonyl group may be either a straight chain or a branched chain, but a straight chain is preferred. Specific examples of the alkoxycarbonyl group include a linear C1 to C6 alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, and a n-propoxycarbonyl group; an isopropoxycarbonyl group and an isobutoxycarbonyl group; And a branched chain C1 to C6 alkoxycarbonyl group such as a second butoxycarbonyl group. As the substituted or unsubstituted C1 to C12 alkyl group in R3 and R4, a substituted or unsubstituted C1 to C6 group is preferred, and a substituted or unsubstituted to C4 alkyl group is more preferred. The substituted C1 to Q2 alkyl group as a substituent 321100 21 200948904, in addition to being a hospital base, may be any of the substituents listed as a substituent on ruthenium and iridium to R4. The number of substituents substituted with a C1 to cl2 alkyl group is usually from 1 to 4, preferably from 1 to 2, and more preferably 1. The alkyl group is preferably an unsubstituted C1 to C12 alkyl group. The alkyl group may be any of a straight chain, a branched chain and a cyclic ring, but a straight chain or a branched chain is preferred, and a straight chain is preferred. Specific examples of the C1 to C12 alkyl group may, for example, be an indenyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a tenth house, and a ruthenium group. a carbon-based straight bond C1 to C12 alkyl; isopropyl, isobutyl, tert-butyl, isopentyl and isohexyl branched chain C1 to C12 alkyl; and cyclopropyl, cyclobutyl, a cyclic C1 to C12 alkyl group such as a cyclopentyl group or a cyclohexyl group. Specific examples of the substituted or unsubstituted amino fluorenyl group in R3 and R4 include, for example, an unsubstituted amino fluorenyl group; and an N,N-didecylamino fluorenyl group, etc. An N-di(C1 to C4)alkylaminocarbenyl group; and an N-arylaminocarbamyl group such as a phenylamino fluorenyl group. Specific examples of the substituted or unsubstituted amine fluorenyl group in R3 and R4 include, for example, an unsubstituted amine thiol group; N-decylamine sulfhydryl group or N,N-dimethylamine sulfonate. N-(C1 to C4)alkylamine sulfonyl or fluorenyl, fluorenyl-di(C1 to C4)alkylamine sulfonyl; and p-carboxyphenylamine sulfonyl hydrazide Substituted aryl-amine sulfonyl and the like. Specific examples of the substituted or unsubstituted amino group in R3 and R4 include, for example, an unsubstituted amino group; an anthracene-fluorenylamino group or an anthracene, a fluorenyl-dimethylamino group or the like (C1 to C4) An alkylamino group or a di(C1 to C4)alkylamino group; an amino mercaptoamine group; and an unsubstituted C1 to C4 mercaptoamine group such as an ethenylamino group. 321100 22 200948904 * The "Cl to Cl2 burning base" in the base of the Cl to Cl2 base can be included in the ruler 3 and r4, including the preferred ones and the examples, and the above-mentioned "R3 and R4" The group described in the section "C1 to C12 alkyl group substituted or unsubstituted". The unsubstituted C1 to C12 alkylsulfonyl group is preferred. Further, specific examples thereof include an ethyl continuation base and the like. Examples of the C1 to C4 alkoxy group in R3 and R4 include a C1 to C12 succinyloxy group such as a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. ® as a suitable R3 and the latter's one is a carboxyl group; an alkoxycarbonyl group; or a substituted or unsubstituted amino group; the other is a chlorine atom; a halogen atom; a carboxyl group; an alkoxycarbonyl group; Substituent; hydroxy; substituted or unsubstituted C1 to C12 alkyl; substituted or unsubstituted amino fluorenyl; substituted or unsubstituted amine sulfonyl; substituted or unsubstituted amine; nitro; C1 to C12 Alkylsulfonyl; or C1 to C4 alkoxy. It is preferable that the other is a hydrogen atom or a halogen atom. When all of the above-mentioned groups and substituents represented by hydrazine have a hydrogen atom, even if the hydrogen atom is substituted by a group other than a hydrogen atom, it is included in the present invention as long as the effects of the present invention can be attained. However, it is usually preferred to not contain the additional substituent. Among the compounds represented by the above formula (1), the compound represented by the above formula (2) is preferred. In the above formula (2), 'R2 to 匕 denote the same meaning as 匕 to 中 in the above formula (1). Specific examples of the above formula to R4 are also the same as the specific examples of R2 to R4 in the above formula (1). 321100 23 200948904 In the above formula (1) and the above formula (2), 'appropriate oxime is: hydroxyl group; amine group; - anthranyl group substituted with a thiol group; unsubstituted anilino group; aryl-alkylamine substituted by a carboxyl group a base (preferably a phenyl C1 to C4 alkylamino group substituted by a carboxyl group); having a selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group, a ketone group, an aminomethyl fluorenyl group, a cyano group, an anilino group, a phenoxy group a group of at least a C1 to C4 alkylaminoalkylamino group (preferably a C1 to C4 alkylamino group of a C1 to C4 alkyl group), an amine group, a hydroxyl group, and a hydrogenthio group. A monoalkylamino group having a substituent as a substituent (except that the alkyl group of the monoalkylamino group is a C1 to C12 alkyl group); or an unsubstituted monoalkylamino group. Further, preferred R2 may, for example, be a halogen atom. A compound in which r2 is a halogen atom can be used as a magenta dye, and a compound in which r2 is a halogen atom can also be used as an intermediate in the synthesis of a compound of the invention wherein R2 is a hydroxyl group or the like. Preferably, R2 is a hydroxyl group; an amine group; an anilino group substituted with a carboxyl group; an unsubstituted amino group; a phenyl C1 to C4 alkyl group substituted with a carboxyl group; and a mono C1 to C12 alkyl group substituted by a carboxyl group. An amine group (preferably a mono C5 to C12 alkylamino group substituted with a carboxyl group); or an unsubstituted monoalkylamino group. Further, g is preferably an example of R2, and examples thereof include a gas atom or a bromine atom. Further, more preferably, R2 is a hydroxyl group; an amine group; a strepto-amino group substituted with a carboxyl group; an unsubstituted anilino group; a phenyl C1 to C4 alkylamino group substituted with a carboxyl group in an alkyl group; and a mono C5 substituted by a carboxyl group C11 alkylamino group; or unsubstituted C5 to Cl1 monoalkylamino group. Meanwhile, as an example of a more preferable R2, 歹ij may be a gas atom or a bromine atom. Particularly preferred R2 is a hydroxy group; an unsubstituted anilino group; a phenyl C1 to C4 alkylamino group having an alkyl group substituted with a thiol group; or a mono C5 to 24 321100 200948904 * C11 alkylamino group substituted with a carboxyl group. - Most preferably R2 is a hydroxy group; or a mono C5 to Cli alkylamino group substituted by a carboxy group. Further, examples of the most preferable R2 include a chlorine atom. ❹ In the above formula (1) and the above formula (2), as a suitable combination of the ruler 3 and the oxime, 'Eith, R3 and h are each a carboxyl group; a mercaptocarbonyl group; i substituted or unsubstituted amino group a mercapto group, the other being a hydrogen atom; a halogen atom; a carboxyl group; an alkoxycarbonyl group; a sulfonic acid group; a hydroxyl group; a substituted or unsubstituted C1 to C12 alkyl group, a substituted or unsubstituted aminomethyl fluorenyl group; Unsubstituted amine sulfonyl; substituted or unsubstituted amine; nitro; diabase; (d) to a combination of alkoxy groups Π 2 filaments with R 3 or R 4 - as a hydrogen atom, a tooth atom, or a combination of counties And one of the parties is a carboxyl group and the other side is a nitrogen shoulder not ten" K3^K4

It is particularly preferable that one of ... is a carboxyl group and a combination of a further sub or a tooth atom is a combination of more I R η μ and S atoms. The substitution position of R3 and 仏 does not have a bamboo residence. When the substitution position is set to 1 position, the system is made by the formula, but the # azo group is 2 digits and the other is 4 digits; _4 = and the other party It is preferably 5, and the combination is preferably 2, and the 3 is 5, and the combination of the suitable position and the 5 position is also included. When the substitution position is determined to be 1 position, it is preferred that the two groups are: when the azo group is unsubstituted or the unsubstituted amino group (tetra) group, and the other one is substituted for the carboxyl group at the 2 position, the south atom. Combination of the drive, · more::: the carboxyl group in the 5 position of the chlorine in the place, the other is the substitution d: - the square is substituted in 2; the best is: one is substituted = atom or functional atom Group of carboxyl groups, the other is a combination of 321100 25 200948904 at the 5-position halogen atom. With respect to the above formula (1) or the formula (2) shown in the formula (2), the substituents and the substitution positions thereof are compounds in which the preferred groups are combined with each other to form a compound which is a better compound. It is especially good. The same applies to compounds and the like which are combined with each other by a particularly preferable group. To specifically cite the appropriate enthalpy of the present invention, the compound is as follows - (1) An enoxa-pyridinone compound which is in the above formula (丨) or the above formula (2) , R 2 is a hydroxyl group; an amine group; an anilino group substituted with a carboxyl group; or a non-fluorene-substituted amino group; a phenyl Ci to C 4 alkylamino group substituted with a aryl group; or a mono C 1 substituted by a carboxyl group a C12 alkylamino group, or an unsubstituted mono C1 to C12 alkylamino group, one of R3 or R4 being a slow or unsubstituted amino fluorenyl group, and the other being a hydrogen atom, a halogen atom, or a thiol group 'In the formula (1), 'h is a hydrogen atom or a methyl group. (ii) ( 吼唆 ketone compound as in (i), wherein R 2 is a hydroxyl group; an unsubstituted anilino group; a substituted phenyl C1 to C4 alkylamino group; or a carboxy substituted single C1 to C12 alkyl amine group. ϋ (iii) as in (i) a pyridinone compound, wherein one of the hydrazine or hydrazine is The other party is a wind atom or a halogen atom. (iv) If (i) or (ii) is a ketone compound, one of the 匕 or 匕 is a rebel, the other For halogen atoms.

Cv) a hydrazine ketone compound according to any one of (i) to (iv), wherein

The substitution position of Rs or R4 is one substitution with respect to the decyl group at the 2 position, and the other substitution with the even I group at the 5 position. 321100 26 200948904, (vi) as in (1), (丨^), (and), and (in addition to any of the phantoms, a compound of the formula wherein R2 is a hydroxyl group or substituted by a thiol group. a single ci to C12 'alkylamino group. (vii) A hydrazide compound of any of (i), (ii), and (Vi), wherein one of R3 or R4 is relative to The azo group is a carboxyl group at the 2-position, and the other is a functional atom at the 5-position relative to the azo group. (viii) An oxime-acridone compound 'is in the formula (1), and Ri is a ruthenium atom or The methyl group 'h is a halogen atom, and one of 1 or r4 is a carboxyl group or an amine group which is not substituted with an amine group, and the other is a hydrogen atom, a halogen atom or a carboxyl group, and preferably one of the Ra or K4 is a carboxyl group. The other one is a hydrogen atom or a halogen atom. Further, as an example of a preferred compound, in the above (), (ix) R2 is a trans group; an unsubstituted anilino group; and a pyridyl moiety is substituted with a few groups. a phenyl C1 to C4 alkylamino group; or a carboxy-substituted mono C5 to C11 oxime-based amine group 'R3 or R4, one of which is a group, and the other is a hydrogen atom or a halogen atom a ketone compound; and (X) fluorene is a group; or a mono C5 to C11 alkylamino group substituted by a carboxyl group, the Rs or I-------------- The acetonide compound having a nitrogen atom of the 5-position is a hydrazine compound of the present invention. The specific examples of the hydrazine-biting compound represented by the above formula (1) of the present invention are shown in the following Table 27 321100 200948904 [Table 1]

Compound n〇_ R 1 R 2 R 3 R 4 1 CH3 OH 2-carboxy 5-C 1 2 CH3 11-carboxyundecylamino group 2-carboxy SC 1 3 CH3 5-drum decylamino 2 -carboxy 5-C! 4 CH3 2-phenyl-1-carboethylamino 2-carboxy 5-C 1 5 CK3 anilino 2-carboxy 5-CI 6 CH3 3-carboxyanilino 2-carboxy 5- C 1 7 CH3 2-ethylhexylamino 2-carboxy SC 1 8 CH3 Amino 2-carboxy 5-C ! 9 CH3 OH 2-carboxyindole 10 CH3 11-carboxyundecylamino 2-carboxyindole 11 CH3 5-Resylpentylamino 2-carboxyindole 12 CK3 2-phenyl-1-carboethylamino 2-carboxyindole 13 CK3 Anilino 2-carboxyindole 14 CH3 3-Acetylamino 2-nonyl group 15 CH3 2-ethylhexylamino 2-carboxyindole 16 CH3 Amino 2-carboxyindole 17 CH3 0H 2-carboxy 4-C 1 18 CH3 11-carboxyundecylamino 2 Carboxyl 4-C 1 19 CH3 5-postylpentyl group 2-carboxyl 4-C 1 20 CH3 2-phenyl-1 - alkylamino 2-carboxy 4-C 1 21 CH3 phenylamino 2- Entyl group 4-C 1 22 CH3 2-ethylhexylamino 2-carboxy 4-C 1 23 CH3 0H 2-aminomethylindenyl 24 CH3 11-carboxyundecylamino 2-amino醢基Η 25 CH3 5-Thetylpentylamino 2-aminomercaptopurine 26 CH3 2-Phenyl-1-Drumethylamino 2-aminocarbazinyl 27 CH3 Anilino 2-aminocarbazinyl Η 2B CH3 OH 3-carboxy 5-carboxy 29 CH3 11-carboxyundecylamino 3 - thiol 5-carboxy 30 Η 0H 2-enyl 5-C 1 31 Η 11-carboxyundecyl Amino 2-carboxy 5-C 1 32 CH3 C 1 2-carboxy 5-C f 33 CH3 C 1 2-carboxyl H The compound represented by the above formula (1) or the above formula (2) is a free acid or .28 321100 200948904 'The form of its salt exists. The salt of the compound of the above formula (1) or the above formula (2) may, for example, be a salt formed with an inorganic or organic cation. Specific examples of the salt formed with the inorganic cation include an ammonium salt or an alkali metal salt (e.g., a salt such as a lithium salt, a sodium salt or a potassium salt). Further, the salt formed with the organic cation may, for example, be a quaternary ammonium salt represented by the following formula (3). The salt of the compound represented by the above formula (1) or the above formula (2) is not limited to such a salt. Z4-N-Z2 (3) Z3 〇 (In the formula (3), 2! to Z4 each independently represent a Cl to C4 alkyl group, a hydroxyl group C1 to C4 alkyl group, or a hydroxyl group C1 to C4 alkoxy group C1 to C4 alkane Base, redundant to at least one of Z4 is a group other than a hydrogen atom). Here, examples of the C1 to C4 alkyl group in the range of Ζι to Z4 include, for example, a methyl group and an ethyl group; and examples of the hydroxy group C1 to C4 alkyl group include, for example, a hydroxymethyl group, a hydroxyethyl group, and a 3-hydroxypropyl group. , 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, etc.; hydroxy C1 to C4 alkoxy C1 to C4 alkyl can be exemplified by: ethoxylation Base group, 2-carbylethoxyethyl group, 3-(p-ethoxyethoxy)propyl group, 3-(p-ethoxyethoxy)butyl group, 2-(p-ethoxyethyl)butyl group, etc. . Among the above-mentioned salts, preferred are, for example, sodium, hexyl, sulfonate, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and/or ammonium. Various salts formed. Among these, various salts formed with lithium, sodium, potassium and/or ammonium are particularly preferred. As is known to those skilled in the art, the salt of the compound represented by the above formula (1) or the above formula (2) can be easily obtained by the following method or the like. For example, in the aqueous solution of the reaction 29 321100 200948904 after the last step in the synthesis reaction of the compound, or by dissolving a wet cake containing the compound or a dried product of the compound, salt is added thereto. Salting out, the precipitated solid is separated by filtration to obtain a sodium salt wet cake of the compound. Further, after the obtained sodium salt wet cake is dissolved in water, an acid such as hydrochloric acid is added to adjust the pH, and the precipitated solid is separated by filtration to obtain the free acid of the compound. Further, in the above method, a mixture of a free acid and a sodium salt of a sodium salt may be obtained in a desired ratio by appropriately adjusting the pH of the aqueous solution by using sodium hydroxide. Further, by adding the wet cake of the free acid of the compound to water, it is possible to add, for example, potassium hydroxide, hydrogen peroxide, ammonia water or a 4- to ammonium salt represented by the above formula (3) while mixing. The hydroxide or the like is made alkaline, and each of the corresponding potassium salt, lithium salt, ammonium salt, or quaternary ammonium salt is obtained. In addition, it is also possible to prepare a mixed salt of a lithium salt and a sodium salt by adjusting the number of moles of each base to the number of moles of the free acid by using two or more kinds of bases to be added. Alternatively, it may be selected from two or three mixed salts of any combination of a lithium salt, a sodium salt, a potassium salt, and an ammonium salt. The salt of the indole pyridone compound of the present invention may have properties such as solubility in physical properties or ink properties as inks, particularly in terms of fastness, depending on the kind of the salt. Changed. Therefore, in order to proceed smoothly, it is preferable to appropriately select the type of salt in accordance with the ink performance and the like as the purpose. The method for producing the compound of the present invention is described below. Meanwhile, 匕 to R4 described in the following formulas (4) to (11) have the same meanings as in the above formula (1). Further, in the following description, the compound of the present invention will be described by the compound of the formula (1): 30321100 200948904 1 , but since the compound of the formula (2) is a preferred compound of the formula (1), the compound of the formula (2) The same is true for China. * For the oxime compound 1 shown in the following formula (4), ethyl benzhydrazide ethyl acetate 1.1 to 3 mol, in a polar solvent such as diphenylbenzene, in the presence of a basic compound such as sodium carbonate Next, a compound represented by the following formula (5) is obtained by reacting at 130 to 180 for 5 to 15 hours.

For the obtained compound 1 mol of the above formula (5), by using m-aminobenzidine, 1 to 5 mol, in an aprotic φ-type polar organic solvent such as N,N-didecyl decylamine The condensation reaction (Ullmann reaction) is carried out at 110 to 150 ° C for 2 to 6 hours in the presence of a sodium carbonate test or the like and a copper catalyst such as copper acetate to obtain the following formula. (6) The compound shown.

31 321100 200948904 The obtained compound of the above formula (6) is sulfonated in 8 to 15% fuming sulfuric acid at 50 to 120 ° C while hydrolyzing the ethyl hydrazino group, thereby obtaining the following A compound of the formula (7).

The obtained compound of the above formula (7) is added to water, and the pH of the reaction liquid is adjusted to 11 to 12 with an aqueous sodium hydroxide solution or the like, and stirred at 60 to 95 ° C to obtain the following formula (8). ) the compound shown.

On the other hand, 1-amino-8-hydroxy-3,6-naphthalene disulfonic acid (H acid) is dissolved in water to 1.0 to 1.2 mol to obtain an aqueous solution of citric acid. Next, in a solution in which 1.0 to 1.2 mol of 2,4,6-trichloro-S-three-pill (Cyanuric Chloride) is suspended in water, it is dropped at 5 ° C or lower. The above aqueous solution of citric acid gives a compound represented by the following formula (9). In the reaction liquid containing the compound represented by the following formula (9), an azo compound having an aniline having R3 and R4 as a substituent obtained by a usual method is added, and the following is maintained at 5 ° C 32 321100 200948904 The compound represented by the following formula (10) is obtained by coupling it.

(1〇) In the reaction liquid containing the compound represented by the above formula (10), the compound represented by the above formula (8) is added, and the reaction is carried out at 20 to 80 ° C and pH 2 to 10 for 1 to 24 hours. 'The compound represented by the following formula (11) is obtained.

Next, 'for the compound of the above formula (11), 1 mole, for the introduction of the group R2, for example, the compound 1 to 4 is shown in the formula, and the pjj2 to 12 and 50 to 1〇(TC) The compound of the formula (1) or / and the formula (2) of the present invention is obtained by reacting for 5 to 5 hours. The obtained compound of the above formula (1) or / and formula (2) of the present invention is After the reaction, by adding a mineral acid such as hydrochloric acid to the reaction solution, the free acid of 33 321 100 200948904 can be isolated, and the obtained free acid solid can be removed by washing with water or an acidic aqueous solution such as hydrochloric acid. An inorganic salt contained in an impurity (for example, a vapor of an alkali metal cation such as sodium vaporate or a sulfate of an alkali metal cation such as sodium sulfate), that is, an "inorganic impurity" in the present specification can be removed. And storage stability of the ink or the like when preparing the ink composition containing the compound represented by the above formula (1) or / and formula (2) as a pigment and/or ink, or inkjet using the ink Recording isochronous discharge stability, etc., often have a bad influence. Therefore, In the total mass of the anthracene compound represented by the above formula (1) or / and formula (2), the content of the inorganic impurities is preferably at least 1% by mass or less, and the lower limit is 0% by mass, that is, It may be below the detection limit of the analysis machine. A method of producing a compound having less inorganic impurities is known, for example, by a reverse osmosis membrane. For other methods, the above formula (1) or / and (2) The dried product or the wet cake of the compound shown is suspended in a mixed solvent of a C1 to C4 alcohol such as decyl alcohol and water, and after stirring, the precipitated solid is separated by filtration, and the inorganic impurities are removed by drying. The compound represented by (1) or / and formula (2) is suitable for the dyeing of natural and synthetic fiber materials or blended products, and is suitable for the manufacture of ink for writing and ink for inkjet recording. It contains the above formula (1) or / The reaction liquid of the compound represented by the formula (2) may be used as it is in the production of the ink composition of the present invention. Further, the reaction liquid may be isolated from the reaction liquid, for example, by a spray drying method or the like. Dried and isolated from the compounds of the invention The obtained compound may be added to 34.321100 200948904 to form an ink composition. The ink composition of the present invention usually contains the above formula (1) as a pigment, relative to the total mass of the ink-filled product. And the compound represented by the formula (2) is from 0.1 to 20% by mass, and preferably from 1 to 0.10% by mass, more preferably from 2 to 8% by mass. The ink composition of the present invention is water-based. The medium is prepared and, if necessary, may contain a water-soluble organic solvent and other ink preparation agents, without departing from the effects of the present invention.

The water-soluble organic solvent is used for the purpose of improving the solubility of the dye, preventing dry welding (maintaining wettability), adjusting viscosity, promoting penetration, adjusting surface tension, and/or defoaming. Other ink preparation agents include, for example, antiseptic and antifungal agents, pH adjusters, chelating agents, anti-money agents, ultraviolet absorbers, viscosity modifiers, dye dissolvers, fading inhibitors, emulsion stabilizers, surface tension Conventional additives such as conditioners, defoamers, sub-(4), and dispersion stabilizers. The total f:1:m organic solvent content of the ink is 0 to the door. The range of m° to 50% by mass is preferably 10 to 3. Better % by mass Please be good, from 3 to 1 () quality ^g to 2g please ’ to 分 to water. 〇〇贝嫂嫂佳. Examples of the residual ethanol in the remainder other than the above may be exemplified by methanol: 3 = to isohydric; alcohol, n-butanol, isobutanol, and second butanol dibutyl S ^ CUC 4 calcined alcohol ( Alcohol); N, N, N-dimercaptoacetamide, etc. 醯-mercaptoamine and ketone, K ketone, "ke-bbi" base phase, !, 3-dimethyl The base is called 2-ketone, 321100 35 200948904 1'3-one base six. a dense w, such as a heterocyclic phase; acetone, mercaptoethyl net, and 2-methyl-2-bromopyrrolidine _4, etc. or alkyl alcohol; tetraammine and a binary ether such as World War II; Alcohol, hydrazine or imum dimethoate, 1,6-hexanediol, diethylene glycol, triethylenedipropylene glycol 'polyethylene di(tetra) propylene glycol, and thiodiglycol coffee c〇i) have C2 to C6 stretch Unit of mono-, oligomeric or (tetra) diol or thioglycol (this 〇 〇 ) 1); glycerol and hexanol triol and other polyols (and triol as your ethylene glycol monomethyl _ Ethylene glycol, single ethylene, ethylene glycol, early nail (four), diethylene glycol monoethyl hydrazine, diethylene glycol monobutyl mystery (also = carbitol), triethylene glycol monomethyl, And triethylene glycol monoethyl sulphate = sacred C1 to C4 monofilament 7 _ _ _ _; or diterpene phenyl hard, etc. 00 of the above water-soluble organic solvents are preferably isopropanol, glycerol , mono- or ethyl alcohol, dipropylene glycol, 2-pyrrolidone, fluorenyl-methyl-2-pyrene, and butyl carbitol, more preferably isopropanol, glycerol, di-alcohol , 2 kisses each bite ketone, Ν-methyl 2 - scale copper, and butyl carbitol. Water-soluble machine _ is (four) or mixed When preparing the ink-based graded product of the present invention, it is preferable to use a water-soluble organic solvent. = For the anti-corrosion and anti-fungal agent, for example, an organic sulfur system, an organic nitrogen sulfur: an organic cryptosystem, a tooth. Aryl lanthanide, iodopropargyl (i〇d-_咖) "'N_hal〇alkylthi〇), benzopyrene, nitrile, π pyridine, I hydroxyquinoline , isothiazolin-based, dithiol (dithi〇i) bond 骧it oxide, nitropropanoid, organotin, lanthanide, grade 4, monoterpene, thiadiazine Anthranil 321100 36 200948904 , system, adamantane, dithiocarbamate, bromoindancme, benzyl bromide, and inorganic salts The organohalogen compound is exemplified by pentachloronaphthalene. The compound of the bite oxide compound is exemplified by 2-pyridyl mercaptan _ 丨 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Isothiazoline-3-yl ketone, 2-n-octyl-4-isoindole-3-indole, 5-chloro-2-methyl-2-isothiazoline-3-oxone, 5-chloro-2- Methyl-4-isothiazolin-3-indole Magnesium chloride, 5-chloro-2-methylpyridyl 4-isothiazolin-3-one calcium chloride, and 2·~methyl-4-isothiazoline-3-yl ketone chlorinated, etc. Examples of the fungicide include sodium sorbate, sodium acetate, and sodium benzoate. Specific examples of the antiseptic and antifungal agent include pr〇xelimi GXL (8) and Pr〇xelKTM XL-2 (S) [trade names, all of which are Avicia. It is preferable that the pH adjuster is used for the purpose of improving the stability of the ink to be stored, as long as it does not adversely affect the ink composition of the present invention and can control the pH of the ink. 6. 〇 to 11. The range of 〇 can be used, and any substance can be used. Examples thereof include alkanolamines such as diethanolamine and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydride, and potassium hydroxide; ammonium hydroxide; or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. Carbonate and the like. Examples of the integration reagents include sodium ethylenediaminetetraacetate, sodium nitrotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and urea0 oxime-ethylamine. Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, and sulfur 37 321100 200948904 diisopropylammonium nitride, ammonium thioglycolate, pentaerythritol tetranitrate, and dicyclohexyl nitrite. The ultraviolet absorber may be used, for example, as a dick-and-triazole-based compound, a cinnamic acid-based compound, a stagnation yttrium compound, a stupid vinyl compound, or a benzoxazole-based compound as a compound. Fluorescent compound, also known as 骜光白白=Absorbing UV in terms of viscosity modifier, 'except water-soluble organic two listed water-soluble polymer compounds' such as polyethylenol, polyamine, and polyimine Wait. ‘·’, 叮, creatures,

As the dye-dissolving agent, for example, urea is used to remove silane, ε-caprolactam, and carbon S-ethylene vinegar, etc., and urea is preferably used.

The color enhancer is used for the purpose of improving the preservation of images. As the fading preventing agent, various organic and metal complexes can be used: the fading preventing agent' organic fading preventing agent is, for example, hydroquinone, alkoxy phenol, dialkoxy phenol, phenol, An aniline, an amine, an indane (^ such as a ^, a chroman, an alkoxyaniline, a heterocyclic, etc.), a chromic preventing agent such as a nickel complex Examples of the surface tension adjuster include interfacial activity, a female anionic surfactant, an amphoteric surfactant, a cationic interfacial activity, and a nonionic surfactant. The agent may, for example, be a silk tree-based acid salt, an α-olefin Wei salt, a polyoxy-extension ethyl silk acid acid salt, an n-glycosyl amino acid and a salt thereof, and an N-mercaptomethyl bovine salt. Silk sulphate polyoxyalkyl ether sulfate, county sulphuric acid county oxygen sulphate _ acid salt, rosin acid 321100 38 200948904 soap, castor oil sulfate, lauryl sulfate, alkyl phenol phosphate, &quot ; alkyl type phosphate, alkyl aryl sulfonate, diethyl sulfosuccinate, two a hexyl sulfosuccinate succinate, a dioctyl sulfosuccinate succinate, etc. Examples of the cationic surfactant include a 2-vinyl π-bite derivative and a poly 4-vinyl pyridine derivative. As the amphoteric surfactant, for example, lauryl dimethylaminoacetic acid sweet lysate, 2 _ ke thiol thiol-N-light ethyl ethyl sigmaline iron betaine, coconut oil fatty acid 醯Aminopropyl dimethylaminoacetic acid betaine, polyoctyl polyaminoethylglycine, and other imidazoline derivatives, etc. As a nonionic surfactant, for example, polyoxyethyl ether Nonylphenyl ether, polyoxyethyl octyl phenyl ether, polyoxyethylene ethyl decyl phenyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl ether ethyl ether ether And ethers such as polyoxyethylene ethyl ether; polyoxyethylene ethyl oleate, polyoxyethylene ethyl distearate, sorbitan laurate, sorbitan monostearate, sorbus An ester such as an anhydride monooleate, a sorbitan sesquioleate, a polyoxyethylene phthalate, and a polyoxyethylidene ester; and 2, 4, 7, 9-tetradecyl _5_癸 fast-4,7_two drunk, 3,6_dimercapto_4_octane-3,6-diol, and 3,5-dimethyl-1 An acetylene glycol (alcohol) such as hexyn-3-ol; etc. Specific examples of the nonionic surfactant include, for example, Surf ynolRTM 104, Surfynol RTM 82, Surfynol RTM 465, and Olfine rtmSTG (trade name, 曰信As a defoamer, a high oxidizing oil system, a glycerin fatty acid vinegar system, a fluorine system, and a polysilicon compound are used as needed. These ink preparations are used alone. In addition, the surface tension of the ink containing the ink set of the invention of the present invention is usually m, preferably 25 to 60 mN/m. Similarly, the order of 溆^N/•·s is preferably adjusted to 2 〇 · 以 ^ ^ ^ 疋 30 = = = = = = = = = = = = = = = = = = = = = = = When modulating ink cartridges, it is preferred to use ion-exchanged water or distilled water to minimize the amount of impurities. Worry water or, if necessary, 'can also remove inclusions from the ink composition by using thin enamel, and use the fine ink to make a precise transition to the second machine. The pore size is usually _ to 〇._, and it is better to consider it. 2.2^m containing the composition of the present invention, which is suitable for use in printing, photocopying, marking 4=ink set or recording (printing), attaching, jin, the ink composition of the present invention The drying of the nozzles of the ink jet printer is also less likely to cause precipitation of crystals, which is liable to cause clogging of the nozzle head. Furthermore, when the mouth is black, and the ink composition is not the same, for water, light 'ozone; 2: Ben:: t have good patience, can get high quality magenta = 2 = ° recorded The water resistance of the image on plain paper is extremely good. ^ In the inkjet printer, two kinds of high-density inks and low-concentration inks are simultaneously loaded into one printer for the purpose of supplying high-definition images. At this time, the ink containing the compound of the present invention as a "," pigment, and the ink contained in a low concentration can be separately prepared, and the inks can be used as an ink set (321100 40 200948904). Further, it is also possible to use only one of the two compounds to contain the compound of the present invention. Any of the j' may not be used to impair the water resistance of the compound of the present invention, and may be used in combination with a conventional magenta. The effect of the present invention can also be used for the purpose of mixing the color grading of other colors (for example, black) with the coloring matter or the cyan pigment to prepare the red ink or (or purple) ink. The coloring body of the present invention refers to the compound of the present invention: The material of the coloring body is not particularly limited, and the coloring matter information conveying sheet, fiber or cloth is used. It is possible to use a substrate such as a substrate to be colored, and it is not limited to such a skin color method, such as a dip dyeing method, a smear printing method, a screen printing squeaking, etc., a method of performing an ink jet printer, etc. Invention 2, the method of the watch machine is ±. W by inkjet printing The above-mentioned information-transferring sheet is not particularly limited, and of course, L, a person can pass through the paper, and a surface-treated person can also be used. Specifically, for example, a substrate such as a paper or a film is provided with an ink. The accommodating layer or the like is provided, for example, by a method of applying a cationic polymer 3 or a method to the above substrate; or a porous oxidizing dream, a method of coating a hydrophilic polymer such as an inorganic fine particle such as a vinyl fluorene and/or a polyethylene chelating net, which is capable of absorbing a pigment in an ink, or a method of coating the surface of the substrate. Equivalent ink accepting capacity = called inkjet paper, inkjet special film, glossy paper, or glossy enamel film, etc. 41 321100 200948904 § Plain paper refers to paper that does not have a special ink receiving layer, depending on the application. A wide variety of papers are sold on the market. When one of the commercially available plain papers is listed, there are two types of high-quality plain paper (made by Seiko-Epson Co., Ltd.) and color plain paper (made by Canon). Multipurpose Paper and ΑΠ-in-one Printing Paper

Hewlett Packard Company); and so on. Others, which are not particularly limited in use, are PPC paper for inkjet printing and the like, and are also plain paper.

The image of the ink composition of the present invention recorded on the plain paper as described above is particularly excellent in water resistance, and is excellent in other light, ozone, humidity or friction. On the other hand, the ink composition of the present invention can also be used for the above-mentioned ink jet paper. The recording of the recorded material by the inkjet printing recording method of the present invention is, for example, mounting a container filled with the ink composition of the present invention at a predetermined position of the ink jet printer, and performing it in an ordinary manner. ,that is,

A method in which a droplet of the ink composition is ejected in response to a recording signal, and is attached to a recording material to be recorded on a recording material. In the inkjet printing method of the present invention, the red ink composition of the present invention can be used alone, and the 'magenta ink can also be formed'. :: color, cyan, green in response to demand, Twilight (or purple) and red are used together with each color of ink. And the various colors of the ink are injected into each of the 'devices' and filled with the installation of the invention (filling the predetermined position of the ink printer, and: in the inkjet printer. From the use of 2 mechanical vibration Piezoelectricity In the ink jet printer, for example, there is a printer using a method of 321100 42 200948904 (Piezoelectricity) and a bubble jet method using bubbles generated by heating. The recording method can use any type of printer. 'The ink composition of the present invention is a vivid magenta color, which is recorded when it is recorded on the mouth black special paper and the plain paper·#recorded material, especially when recorded on plain paper. The high degree of sharpness 'has the hue suitable for the ink jet recording method. In addition, the fastness of the recorded image, especially the water resistance in plain paper is very high and characteristic. The door ",, and the ink composition of the present invention There is no precipitation or separation of a pigment component during storage, and when the ink composition of the present invention is used in inkjet recording, it is very difficult to precipitate crystals due to drying of the ink composition in the vicinity of the nozzle. will not Plug ejector (ink head). The ink composition of the present invention recirculates ink for a longer period of time even when used in a continuous ink jet printer (4), or in an inkjet type on demand When the printer is used intermittently, there is no change in physical properties. 实施 Embodiments Hereinafter, the present invention will be more specifically described by way of examples. Meanwhile, "tu" in the present text has no special description, that is, quality. In the examples, the operation of =W and crystallization, etc., unless otherwise specified, (4) is carried out under the weight of the drop. Meanwhile, in the measurement of the embodiment, in the measurement of the maximum absorption wavelength u, Then, the difference is almost the same as the absorption intensity, which is in the aqueous solution, and is self-recorded as the maximum absorption wavelength. 321100 43 200948904 In addition, any compound of the compound of the present invention synthesized exhibits a solubility of 100 g/L or more.份份份乙乙乙乙乙乙乙144. After 0 parts, raise the liquid temperature at 140 to 1 The reaction is carried out for 8 hours at a temperature of 50 ° C. During this period, the xylene is azeotroped with the ethanol and water formed by the reaction, and the reaction is completed outside the system. Next, the reaction liquid is cooled. After adding 240 parts of sterol at 30 ° C, the mixture was stirred for 30 minutes, and the precipitated solid was separated by filtration. The obtained solid was washed with 360 parts of methanol, and then dried to obtain the following formula (13). Compound 124. 8 parts of pale yellow needle crystals.

(2), a mixture of the compound of the above formula (13): 8 parts, m-aminoacetanilide 75.0 parts, After the copper acetate monohydrate 24.01 parts and the sodium carbonate 12.8 parts, the liquid temperature was raised to 120 to 130 ° C, and the reaction was carried out for 3 hours. The reaction solution was cooled to about 50 ° C, and 120 parts of sterol was added thereto and stirred for 30 minutes. Filtration 44 321100 . 200948904 Separation of precipitated solids. The obtained solid was washed with 500 parts of decyl alcohol and then with warm water of 80 ° C, and dried to obtain a compound of the following formula (14): 79 parts with a blue tint Red solid.

X7 v (3) In 130 parts of 98% sulfuric acid, on the side of the mixture, one side was added with 28 parts of 28% fuming sulfuric acid on the side of water to prepare 300 parts of 12% fuming sulfuric acid. 51.3 parts of the compound represented by the above formula (14) was added thereto at a liquid temperature of 50 ° C or less under water cooling. The liquid temperature was raised to 85 to 90 ° C for 4 hours. The reaction liquid was added to 6 parts of ice water, and the temperature of the liquid due to heat generation was suppressed by adding ice between the reactions, and the liquid temperature was kept below 40 °C. Further, water was added to the reaction solution to make the amount of the liquid up to 1 part, and then the insoluble matter was removed by filtration. Warm water was added to the obtained mother liquid to make 15 parts of the liquid while maintaining the liquid temperature at 60 to 65. (:, adding 300 parts of sodium hydride and stirring for 2 hours) The solid which precipitated was separated by filtration. The obtained solid was washed with 300 parts of a 2% aqueous sodium chloride solution, and the water was sufficiently extracted to obtain the following formula ( 15) Compound 59. 2 parts of 129. 0 parts of wet cake, which is a red solid. 321100 45 200948904

(4) In 500 parts of water, 320 parts of the wet cake of the compound represented by the above formula (15) obtained in the above (3), followed by adding a 25% aqueous solution of sodium cerium oxide to adjust the pH to 12, at 90 ° C The reaction was carried out for 6 hours at the liquid temperature. The reaction solution was filtered, and 400 parts of water was added to the obtained wet cake to adjust the pH to 7, and the precipitated solid was separated by filtration. The obtained wet cake was dried to obtain 85.8 parts of the compound of the formula (16) below.

(5) Adding 19.8 parts of 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid (H acid) to 75 parts of water, followed by adding 25% sodium cerium oxide to adjust the pH to 9 to 9 5. Dissolve the tannic acid. On the other hand, 0.5 parts of Lipal ΟΗ (trade name, anionic surfactant, manufactured by Japan Lion Co., Ltd.) was added to 75 parts of ice water, followed by 10. ◦Cyanuric Chloride, and stirred for 30 minutes. . The citric acid aqueous solution obtained above was kept at a liquid temperature of 0 to 5 ° C while being dripped for 1 hour. Further, the mixture was reacted at a liquid temperature of 0 to 5 ° C for 2 hours to obtain a reaction containing a compound represented by the following formula (17): 46321100 200948904 液.

(17) (6) 8.2 parts of 2-amino-4-chlorobenzoic acid is subjected to azotization by a usual method. The reaction solution is added to the above-mentioned reaction containing the compound represented by the formula (17). In the liquid, one side is maintained at Ο to 5. The liquid temperature of the crucible is further adjusted by adding a 25% aqueous solution of sodium cerium oxide to adjust the pH to 7, thereby reacting the azo compound of 2-amino-4-chlorobenzoic acid with the compound of (17). A reaction liquid of the compound represented by the formula (18).

(18) (In the reaction liquid containing the compound of the above formula (丨8) obtained in the above (6), 'the compound represented by the above formula (16) obtained by adding the first embodiment (4) is added. Next, a 25% aqueous sodium hydroxide solution was added to adjust the pH to 8 to 9, and heating was carried out so that the liquid temperature became 4 〇〇c and the reaction was carried out for an hour, whereby a reaction liquid containing a compound represented by the following formula (20) was obtained. The compound is obtained as a solid by salting out and filtration by a conventional method. λ max : 514 nm 47 321100 200948904

(8), in the reaction liquid containing the compound of the above formula (20), the 25% aqueous solution of sodium hydroxide is added dropwise to maintain a pH of 10.8 to 11.2, one side at 90 to 95 ° The reaction was carried out at a liquid temperature of C for 2 hours. After the reaction, the crystals were precipitated by adjusting the pH of the reaction mixture to 4.0. The precipitated crystal was separated by filtration to obtain a red wet cake of the compound represented by the following formula (22): 80.8 parts.

(9) After the wet cake obtained in the above (8) was added to 500 parts of water, the liquid temperature was adjusted to 50 ° C, and it was dissolved by adding an aqueous ammonia solution. Next, 35% hydrochloric acid was dropped to adjust the pH to 5, whereby crystals were precipitated, and the precipitated crystals were separated by filtration. The obtained wet cake was heated with 600 parts of decyl alcohol, and while maintaining the liquid temperature at 50 ° C for 30 minutes while stirring, the solid was separated by filtration. The obtained solid was washed with 100 parts of decyl alcohol, and dried to give 18.1 parts of an ammonium salt of the compound of the above formula (22), which was red 48 321100 200948904 color solid. ' λ max : 515 nm * Example 2 (1) In the reaction liquid containing the compound represented by the above formula (20) obtained in the same manner as in the treatment of (1) to (7) of Example i, an amine group 12 was added. Alkanoic acid 16.1 parts. In the reaction liquid, a 25% aqueous sodium hydroxide solution was dropped on the surface to maintain the pH at 9 to 10, and the surface was reacted at a temperature of 50 to Torr for 2 hours. After the reaction, the pH of the reaction mixture was 5 (), and the crystals were precipitated, and the precipitated crystals were separated by filtration, and the red wet cake of the compound of the following formula (23) was obtained.

(2) The wet cake containing the compound of the formula (23) obtained in the above (1) was added to 500 parts of water, and the liquid temperature was adjusted to 5 Torr, and then an aqueous ammonia solution was added thereto to dissolve. Next, 35% hydrochloric acid was added dropwise to adjust ρ 到 to 5 to precipitate crystals, and the precipitated crystals were separated by filtration. The obtained wet cake was heated with 6 parts of an alcohol, and maintained at a liquid temperature of 50 ° while stirring for 3 hours, and the solid was separated by filtration. The obtained solid was washed with 1 part of methanol, and dried to give a purified product of the ammonium salt of the compound of the above formula (23) to 25.5 parts of which was a red solid. 321100 49 200948904 Into max: 515 nm Example 3 (1) In the reaction liquid containing the compound represented by the above formula (20) obtained in the same manner as in the above (1) to (7), DL-benzene was added. 4份。 A propylamine. In the reaction liquid, a 25% aqueous sodium hydroxide solution was dropped on the surface to maintain the pH at 9 to 10, and the reaction was carried out at a temperature of 50 to 70 ° C for 2 hours. 5份。 After the reaction, the reaction solution was adjusted to a pH of 5.0 to precipitate crystals, the precipitated crystals were separated by filtration to give a red wet cake of the compound of the following formula (24) 90. 5 parts.

(2) The wet cake containing the compound of the formula (24) obtained in the above (1) was added to 500 parts of water, adjusted to 50 ° C, and then dissolved in an aqueous ammonia solution. Next, 35% hydrochloric acid was dropped and the pH was adjusted to 5 to precipitate crystals, and the precipitated crystals were separated by filtration. The obtained wet cake was heated with 600 parts of decyl alcohol, and while maintaining at a liquid temperature of 50 ° C for 30 minutes while stirring, the solid was separated by filtration. The obtained solid was washed with 100 parts of methanol, and dried to give a purified product of the ammonium salt of the compound of the above formula (24): 23. 4 parts, 50 321 100 200948904 was a red solid. λ max : 515 nm, 551 nm Example 4 (1) In the reaction liquid containing the compound represented by the above formula (20) obtained in the same manner as in the examples (1) to (7), an amine group is added. 9 8 parts of hexanoic acid. In the reaction liquid, a 25% aqueous sodium hydroxide solution was dropped on one side and the pH was maintained at 9 to 10 Å while reacting at a temperature of 50 to 70 ° C for 2 hours. After the reaction, the crystals were precipitated by adjusting the pH of the reaction mixture to 5.0. The lyophilized cake of the compound of the following formula (25) was obtained in an amount of 82.7 parts.

(2) The wet filter of the compound of the formula (25) obtained in the above (1) and the cake were added to 5 parts of water to adjust to 50 ° C, and then an aqueous ammonia solution was added thereto to dissolve. Next, the pH was adjusted to 5 by dropping 35% hydrochloric acid to precipitate crystals, and the precipitated crystals were separated by filtration. The obtained wet cake was heated with 6 parts of decyl alcohol, and kept at a liquid temperature of 50 ° C for 3 minutes while stirring, and the solid was separated by filtration. The obtained solid was washed with 100 parts of methanol, and dried to give 18.9 parts of a purified product of the compound of the compound of the above formula (25) as a red solid. 5份substituted 2-amino-4-chlorobenzene, in addition to the use of anthrani 1 ic acid, 6.5 parts of 2-amino-4-chlorobenzene Other than formic acid, the same treatment as in the above (1) to (6) of Example 1 was carried out to obtain a reaction liquid containing a compound represented by the following formula (19).

(2) In the embodiment (7), except that the reaction liquid containing the compound represented by the above formula (19) obtained above is used in place of the reaction liquid containing the compound represented by the above formula (18), The same as (7), a reaction liquid containing a compound represented by the following formula (21) is obtained.

(3) In the reaction solution containing the compound of the above formula (21), the above-mentioned aniline was added in an amount of 7.0 parts, and the mixture was reacted at a temperature of 50 to 70 ° C for 2 hours. After the reaction, the pH of the reaction mixture was adjusted to 5.0, and 30 parts of ammonium chloride was added thereto to precipitate a solid. The red wet cake of the compound of the following formula (26) was obtained in a ratio of 50.7 parts. 52 321100 200948904

(4) The wet cake of the compound of the formula (26) obtained in the above (3) was added to 600 parts of methanol, heated to 50 ° C and stirred for 30 minutes, and then the solid body was separated by filtration. The obtained solid was washed with 100 parts of decyl alcohol, and dried to give 15.5 parts of a crude product of the compound of the above formula (26), which was a red solid. 5 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 The reaction was carried out at a temperature of 50 Q to 70 ° C for 2 hours. The pH of the reaction mixture was adjusted to 5.0, and 30 parts of ammonium chloride was added thereto to precipitate crystals. The red wet cake of the compound of the following formula (27) was obtained in a ratio of 64. 7 parts.

53 321100 200948904 (2) The wet cake obtained in the above (1) was heated, stirred, and kept at 50 ° C for 30 minutes, and the solid was separated by filtration. The obtained solid was washed with 100 parts of methanol, and dried to give 16.0 parts of a purified product of the compound of the above formula (27) as a red solid. λ max · 518 nm, 557 nm Examples 7 to 12 (A) Preparation of Ink The components of the compound of the formula (22) obtained in the above Example 1 and other ink preparations, etc., are shown in Table 2 below. The composition ratios shown are mixed to obtain the ink composition of the present invention. The resulting ink composition was subjected to ruthenium removal by a 遽.45 // m film filter to obtain an ink for evaluation. Further, the water was ion-exchanged water, and the pH of the ink composition was adjusted to about 9.0 with ammonia water, and water was added to make the total amount 100 parts. The modulation of this ink was taken as Example 7. Similarly, each of the inks having the same composition and operation as in Example 7 was used as Examples 8 to 12 except that the compounds obtained in Examples 2 to 6 were used.份份份份份份份。 0. 0 parts of the compound of the formula (22) obtained in Example 1. 4. 0 parts of glycerol 5. 0 parts of urea 5.0 parts of N-methyl-2-pyrrolidone 4. 0 Isopropyl alcohol 3. 0 parts butyl carbitol 2. 0 parts trade name SurfynolRTM 104PG50C Note) 0. 1 part 54 321100 200948904 Ammonia water + hydration. 76. 9 parts 100. 0 parts (Note) Acetylene glycol system Non-ionic surfactant, Comparative Example 1 manufactured by Kwong Sung Chemical Co., Ltd. In place of the compound of the above formula (22) obtained in the above (8) of Example 1 except that the No. 4 compound obtained in Example 2 of Patent Document 1 was used. The printing ink composition for comparison was prepared in the same manner as in Example 7 except that the coloring matter was used. The modulation of this ink was taken as Comparative Example 1. The structural formula of the pigment used is expressed by the following formula (28). Meanwhile, a compound represented by the following formula (28) is synthesized and used as an ammonium salt.

0 (B) Inkjet printing Using an inkjet printer (manufactured by Canon Co., Ltd., trade name: PIXUSRTM ip 4100), the results of Examples 7 to 12 and Comparative Example 1 were carried out on four kinds of plain papers shown in Table 3 below. Inkjet recording of the modulated ink. In the inkjet recording, a checkered pattern (a pattern in which a square having a concentration of 1.00% and a side of 0% of 1. 5 mm is combined with each other) is produced, and a magenta-white print having a high contrast ratio is obtained. . Further, the white portion is the texture portion of the unprinted plain paper. Further, an image pattern is obtained in such a manner that the color tone of the plurality of levels is arranged in accordance with the reflection density, and a print having a magenta gradation of 55 321100 200948904 is obtained. Further, the printed matter having the gradation of each of the examples and the comparative examples thus obtained was obtained by using L*, a* of the following colorimetric system for the image near the reflection density (D value). The results of the measurement of b* and the difference of C* indicate that any of the inkjet magenta has an appropriate hue and vividness. Further, in the visual judgment of the water resistance test 1 (impregnation test), a checkered printed matter was used as a test piece. In addition, the measurement of the residual color of the water resistance test 2 (wiping test) uses a printed matter having a gradation as a test piece, and the reflection density D value of the printed matter before the test is closest to 1. Determination. The reflection density was measured using a color measurement system (manufactured by Gretag Macbeth Co., Ltd., trade name Sectro Eye). The various S-test methods and evaluation methods of the test results of the recorded images are as follows. Table 3 Plain paper 1

Canon company name: LBP PAPER LS-500 plain paper 2

Hewlett Packard Company Name: Multipurpose Paper Plain Paper 3

Hewlett Packard Company name: All-in-0ne Printing Paper 56 321100 200948904 1 Plain paper 4 4 Canon company name: Office Planner Multigrade (C) Water resistance test 1 (impregnation test) will be recorded after inkjet printing Each of the test pieces of each of Examples and Comparative Example 1 which had been dried for 24 hours was immersed in ion-exchanged water for 1 hour. The test piece was taken out from the water and dried to visually evaluate the color drop of the colored portion of the pattern, and was evaluated into 3 classes on the basis of the following. Slightly faded..........〇 Although it fades, it still has coloring.····

All faded.......... X The results are shown in Table 4. (D) Water-storage test 2 (wiping test) One drop of ion-exchanged water was dropped on each test piece which had been dried for 24 hours after recording by ink-jet printing, and the water-drop was wiped off after one minute. After the test Q pieces were dried, the reflection density was measured using the aforementioned colorimetric system. After the measurement, (reflection concentration after the test/reflection concentration before the test) χ 100 (« calculate the residual ratio of the dye. The results obtained are shown in Table 5. Further, the larger the value, the larger the value The better the result. 57 321100 200948904 Table 4 results of water resistance test 1

Table 5 Results of Water Resistance Test 2 Plain Paper 1 Plain Paper 2 Example 7 74.8 69. 0 Example 8 76. 3 94. 4 Poor Example 9 66. 7 95. 2 —-------- 67 0 Example 10 Γ Ι 7Γ~ Example 11 1 — _ 72.4 ~~1ΪΤ9~ Example 12 Comparative Example 1 71. 3 56. 3 —----------- 70. 2 73.4 64. 4 (4) Medium, the species is △, the water resistance is the most excellent == is 〇 'only the remaining one is - and the other examples 7 to 1 〇 Fang Shen a point 丨 12 series are all △ in 4 kinds of plain paper, and 2 Plain paper is better. Chuanmu than, this correction of the ink and ink in the water resistance \ m 4 kinds of plain paper 14 money 2, in the comparison of wealth, 4 kinds of ordinary three of the residual rate is five + 逋疋 g 逋疋 fifty four or six More than ten% is at 7〇% to 321100 58 200948904 # ο , the residual rate is only seventy percent of the 'only in the present invention even in the worst residual rate of Example 12' in 4 kinds of plain paper Also in the above, in the examples 7, 9 and 1 ', although each of the plain papers is 69. 〇%, 66.7 % and 67.0%, and the latter half of the sixty, but the other three The plain paper is more than 70%' and the residual rate is almost the same as that of the two types of plain paper, or almost 9G% or more. For the eighth embodiment, only one plain paper is used. Seventy percent, the remaining three kinds of plain papers each have eighty percent and the remaining two are on nine breaks. Therefore, it is judged that the ink of the present invention has a remarkable excellent pair in the water resistance test 2. Water-based. That is, with respect to the comparative example, the embodiment? The recorded image of 12 to the visual and color-measurement results are all the same as the plain paper of the comparative example 1 and the rest of the paper, which shows that the water-resistant pole A is superior to that of the comparative example 1 The dye and the ink containing the pigment are recorded in an ink jet or the like. From the above results, it is understood that the above formula (1) of the present invention is based on the viewpoint of water-based, and is resistant to m., δΛ, The carbon number of the base portion is preferably the larger. L industry availability] From the above, the system can be applied to the water-soluble benefit of the inkjet month. Compared with the ketone-combined ink composition, the image of various fast-solubility images is extremely excellent in water resistance and water, and has a good vivid color when it is magenta. Therefore, it is very useful for coloring pigments for various types of recording inks. ,, ink pigments, especially as magenta for inkjet inks 59 321100 200948904 [Simple description of the diagram] None [Main component symbol description

Claims (1)

200948904 4 VII. Patent application scope: 4 1. An indolopyridone compound or a salt thereof, which is represented by the following formula (1), © (wherein 'R1 denotes a halogen atom, a substituent group, a thiol group, a cyclohexyl group, a mono or dialkylaminoalkyl group, or a cyano lower alkyl group, R2 represents a radical, an alkoxy group; an amine group ;_Atom; having a group selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group, an aminomethyl fluorenyl group, a cyano group, an alkyl group, an anilino group, a phenoxy group, an amine group, a hydroxyl group, and a thiol group; An anilino group having at least one substituent as a substituent; an unsubstituted anilino group; having at least one selected from the group consisting of a sulfonic acid group, a carboxyl group, an alkoxy group, a ketone group, an amino group, a cyano group, and a hydroxyl group; An arylalkylamino group as a substituent, an unsubstituted arylamino group; having a selected from the group consisting of an acid group, a buffer group, an alkoxy group, a ketone group, an amine group, a cyano group, an anilino group a phenoxy group, a hydroxy C1 to C4 alkylamino group, a bis(C1 to C4)alkylamino group, an amine group, a hydroxyl group, and a hydrogenthio group, at least one group in the group as a substituent or a single or two An alkylamino group; an unsubstituted mono or dialkylamino group, R3 and R4 each independently represent a chlorine atom; a halogen atom; a fluorenyl group; a oxycarbonyl group; an acid group; Substituted or unsubstituted C1 to C12 alkyl; substituted or unsubstituted amino fluorenyl; substituted or unsubstituted amine 321100 61 200948904 sulfonyl; substituted or unsubstituted amine; nitro; C1 to Cl2 a sulfonyl group; or a C1 to C4 alkoxy group). * 2. The pyridone compound or a salt thereof according to the first aspect of the patent application, wherein R2 is a hydroxyl group; an alkoxy group; an amine group; having a selected from a sulfonic acid group, a carboxyl group, an alkoxy group, an amine group An anilino group having a substituent in the group consisting of a methyl group, a cyano group, an alkyl group, an anthranyl group, a phenoxy group, an amine group, a hydroxyl group, and a hydrogenthio group; an unsubstituted anilino group; An arylalkylamine group having an acid group, a carboxyl group, an alkoxy group, a ketone group, an aminocarbamyl group, a cyano group, and a group in the group of a group as a substituent; an unsubstituted aromatic amine group ® has a choice from a sulfonic acid group, a carboxyl group, an alkoxy group, a ketone group, an amine fluorenyl group, a cyano group, an anthranyl group, a phenoxy group, a thiol group based on a C1 to C4 group, and a bis (C1 to C4 group) a mono- or dialkylamino group as a substituent in the group of an alkylamino group, an amine group, a hydroxyl group, and a hydrogenthio group; or an unsubstituted mono- or dialkylamino group. 3. The hydrazine pyridinium compound or a salt thereof according to the second aspect of the patent application, wherein R! is a hydrogen atom or a methyl group. ❹ 4. As claimed in the second paragraph of the patent application, the pyridine compound or a salt thereof, wherein R! represents a hydrogen atom or a fluorenyl group, and either one of R3 or R4 is a carboxyl group; an alkoxycarbonyl group; or a substituted or Unsubstituted aminomethanyl group, the other being a hydrogen atom; a halogen atom; a carboxyl group; an alkoxycarbonyl group; a sulfonic acid group; a hydroxyl group; a substituted or unsubstituted C1 to C12 alkyl group; a substituted or unsubstituted amine group Mercapto; substituted or unsubstituted amine yellow wine; substituted or unsubstituted amine, nitrate', C1 to C12 alkyl 62 321100 200948904 sulfonyl; ring C1 to C4 alkoxy. ' is as shown in the following formula (2), ' (wherein, 1^, heart and R4 represent the same meanings as in the second paragraph of the patent application, R3 and R4). 6. 6. If the formula is in the range of item 5, and the ratio of the ketone compound or its salt, Wherein, either one of R3 or R4 is a carboxyl group; an alkoxycarbonyl group; or a substituted or unsubstituted thiol group; the other is a hydrogen atom; a halogen atom; a thiol group; an alkoxycarbonyl group; a carboxylic acid group; r substituted or unsubstituted C1 to c12 ❹ 6 group; * silk substituted for mercapto; substituted or unsubstituted amine fluorenyl; substituted or unsubstituted amine; nitro; C1 to C12 alkyl Awake base; or C1 to C4 alkoxylate. • 5. As claimed in the second paragraph of the patent application, pyridine _ compound or its sleeping, 〇7. 申请 艰 酮 蒽 蒽 蒽 蒽 蒽 蒽 蒽 蒽 蒽 蒽 艰 艰 艰 艰 酮 酮 酮 酮 酮An anthranyl group substituted with a radical; an unsubstituted amino group, a aryl group substituted by a fluorenyl group; having an alkyl group selected from the group consisting of a carboxylic acid group, a carboxyl group, an alkoxy group, a ketone group, and an amine group a monoalkylamino group having at least one group of a cyano group, an anilino group, a phenoxy group, a hydroxy group C1 to C4 alkylamino group, an amine group, a hydroxyl group, and a hydrogenthio group as a substituent; or 321100 63 200948904 Unsubstituted monoalkylamino group. 8. The pyridone compound or a salt thereof according to the fifth aspect of the patent application, wherein R2 is a hydroxyl group; an amine group; a strepto-amino group substituted with a carboxyl group; an unsubstituted anilino group; and an alkyl group substituted with a carboxyl group a C1 to C4 alkylamino group; a mono C1 to C12 alkylamino group substituted by a carboxyl group; or an unsubstituted monoalkylamino group, one of R3 or R4 being a carboxyl group or an unsubstituted aminocarbamyl group, and One of them is a hydrogen atom, a halogen atom or a tracing group. 9. The pyridone compound or a salt thereof according to the fifth aspect of the patent application, wherein R2 is a hydroxyl group; an amine group; an anilino group substituted with a carboxyl group; an unsubstituted anilino group; a phenyl group having an alkyl group substituted with a carboxyl group a C1 to C4 alkylamino group; a mono C5 to C11 alkylamino group substituted by a carboxyl group; or an unsubstituted C5 to C11 monoalkylamino group, one of R3 and R4 being a carboxyl group, and the other being a hydrogen atom or a halogen atom . 10. The pyridone compound or a salt thereof according to item 5 of the patent application, wherein R2 is a hydroxyl group; an unsubstituted anilino group; a phenyl C1 to C4 alkylamino group having an alkyl moiety substituted by a carboxyl group; A single C5 to C11 alkylamino group substituted by a carboxyl group, one of R3 and R4 is a slow group, and the other is a halogen atom or a halogen atom. An ink composition comprising the indole-pyridinone compound or a salt thereof as the dye of the second, fifth, eighth or tenth aspect of the patent application, and further comprising water. 12. The ink composition according to claim 11 of the patent application, which further comprises a water-soluble organic solvent. 64 321100 200948904 y ' 13. A composition for inkjet recording ink containing the indolinone compound or a salt thereof as a pigment in the second or the tenth aspect of the patent application, and containing water and a water-soluble organic compound Solvent. 14. In the ink composition of claim 13 of the patent application, wherein the content of the inorganic impurities in the total mass of the acridinone compound in the second or the tenth of the patent application range contained as a pigment is 1 mass ° / 〇 below. The content of the anthrapyridone compound is in the range of 0.1 to 20% by mass, based on the total mass of the ink composition. 16. An ink jet recording method characterized by: ejecting a droplet of an ink composition containing an anthrapyridone compound of claim 2 or a salt thereof, and attaching it to a recording signal Recorded by the recorded material. 17. The inkjet recording method of claim 16, wherein the recorded material is a sheet for information transmission. 18. The inkjet recording method according to the seventeenth aspect of the invention, wherein the sheet for information transmission is plain paper or a sheet for information transmission comprising an ink receiving layer containing a porous white inorganic substance. 19. A coloring body comprising an ink composition comprising both a ketone compound or a salt thereof and a water or water and a water-soluble organic solvent, which are contained in the second or the tenth aspect of the patent application; Shader. 20. The color body of claim 19, wherein the coloring is performed by an ink jet printer. 65 321100 200948904 馨 21. An inkjet printer loaded with a hydrazine and a ketone compound or a salt thereof containing the water and water-soluble organic solvent of the second or first aspect of the patent application. A container of ink composition. 2. The fluorenone compound or a salt thereof according to the first aspect of the invention, wherein 'R! is a methyl group and r2 is a halogen atom. 23. The fluorenone compound or a salt thereof according to claim 22, wherein one of R3 or R4 is a carboxyl group and the other is a hydrogen atom or a halogen 321100 66 200948904 IV. Designated representative map: There is no schema in this case (1) The representative representative map of this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 321100