JP2017137463A - Compound, ink, ink cartridge, and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound useful as a color material which has a preferable hue in the region from magenta to blue and is excellent in light fastness.SOLUTION: The compound is represented by the general formula (1) in the figure. (In general formula (1), at least one of Rand Rrepresents a specific acylamino group.)SELECTED DRAWING: None

Description

  The present invention relates to a novel compound useful as a color material, an ink containing the compound, and the like.

  As a colorant having a magenta hue and good color developability, a compound having a xanthene skeleton is known. A compound having a xanthene skeleton has two high absorption bands (x-band and y-band) in the visible region, and the complementary color of x-band on the long wavelength side and y-band on the shorter wavelength side overlaps, In order to develop a visible color tone, the color developability is good. Among the compounds having a xanthene skeleton, C.I. I. Acid Red 52 and C.I. I. Acid Red 289 is widely known as a color material having a magenta hue and having very good color developability and transparency.

  However, C.I. I. Acid Red 52 and C.I. I. A conventional compound having a xanthene skeleton represented by Acid Red 289 has a problem that light resistance is inferior. In order to improve the light resistance of a compound having a xanthene skeleton, the structure has been improved (see Patent Documents 1 to 7).

JP 09-241553 A JP-A-51-087534 International Publication No. 2013/031428 International Publication No. 2013/031838 JP 2011-148773 A JP 2013-133394 A JP 2013-249339 A

  The level required for color developability and light resistance in the magenta to blue region is increasing year by year, but magenta color materials having a xanthene skeleton still cannot meet the above requirements.

  Accordingly, an object of the present invention is to provide a compound useful as a coloring material having a preferable hue in a magenta to blue region and having excellent light resistance. Another object of the present invention is to provide an ink using the compound, an ink cartridge using the ink, and an ink jet recording method.

  The above object is achieved by the present invention described below. That is, the compound according to the present invention is represented by the following general formula (1).

(In General Formula (1), R ₁ , R ₅ , R ₆ and R ₁₀ each independently represents an alkyl group, a sulfonic acid group, or a halogen atom. R ₂ , R ₄ , R ₇ and R ₉ are each Independently represents a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and R ₃ and R ₈ are each independently represented by a hydrogen atom, an alkyl group, a sulfonic acid group, or the following general formula (2). And at least one of R ₃ and R ₈ is a group represented by the following general formula (2): Z independently represents a sulfonic acid group or a sulfamoyl group, and R ₁ to R ₁₀ When at least one has an ionic group, n represents an integer of 0 to 6, and when R ₁ to R ₁₀ do not have an ionic group, n represents an integer of more than 0 and 6 or less, Z In the general formula (1) Substituted at the position of at least one of the hydrogen atoms of incense ring.)

(In the general formula (2), R ₁₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or a heterocyclic group. * Represents a bonding site with the aromatic ring of the general formula (1). Represents.)

  According to the present invention, it is possible to provide a compound useful as a coloring material having a preferable hue in a magenta to blue region and having excellent light resistance. In addition, according to the present invention, an ink using the compound, an ink cartridge using the ink, and an ink jet recording method can be provided.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. In the present invention, when the compound is a salt, at least a part of the salt may be dissociated into ions in an aqueous liquid such as water or ink, but it is expressed as “salt” for convenience. Further, “n” attached to the alkyl group represents a straight chain.

<Compound represented by the general formula (1)>
As a result of the study, the present inventors have found a compound represented by the following general formula (1) as a compound having a preferable hue in a magenta to blue region and having excellent light resistance. In the benzene ring bonded to the xanthene skeleton via an amino group, the compound represented by the general formula (1) has an alkyl group, a sulfonic acid group, or a halogen atom in the ortho position based on the bonding position of the amino group. The specific substituent is substituted at least at any position of the para-position. In the general formula (1), R ₁ , R ₅ , R ₆ and R ₁₀ are ortho positions, R ₂ , R ₄ , R ₇ and R ₉ are meta positions, and R ₃ and R ₈ are It is a para position. This compound is characterized by having a preferable hue in the magenta to blue region because the group represented by the general formula (1) which is an acylamino group is substituted at the para position.

(In General Formula (1), R ₁ , R ₅ , R ₆ and R ₁₀ each independently represents an alkyl group, a sulfonic acid group, or a halogen atom. R ₂ , R ₄ , R ₇ and R ₉ are each Independently represents a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and R ₃ and R ₈ are each independently represented by a hydrogen atom, an alkyl group, a sulfonic acid group, or the following general formula (2). And at least one of R ₃ and R ₈ is a group represented by the following general formula (2): Z independently represents a sulfonic acid group or a sulfamoyl group, and R ₁ to R ₁₀ When at least one has an ionic group, n represents an integer of 0 to 6, and when R ₁ to R ₁₀ do not have an ionic group, n represents an integer of more than 0 and 6 or less, Z In the general formula (1) Substituted at the position of at least one of the hydrogen atoms of incense ring.)

(In the general formula (2), R ₁₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or a heterocyclic group. * Represents a bonding site with the aromatic ring of the general formula (1). Represents.)

In general formula (1), R ₁ , R ₅ , R ₆ and R ₁₀ each independently represents an alkyl group, a sulfonic acid group, or a halogen atom.
Examples of the alkyl group for R ₁ , R ₅ , R _6, and R ₁₀ include linear or branched alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. The alkyl groups of R ₁ , R ₅ , R ₆ and R ₁₀ may have a substituent as long as the hue and light resistance of the compound represented by the general formula (1) are not impaired. Examples of such a substituent include a hydroxy group; an alkoxy group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group; a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; Can be mentioned. Examples of the alkyl group represented by R ₁ , R ₅ , R ₆ and R ₁₀ include those having a substituent, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, unsubstituted alkyl groups such as sec-butyl group, tert-butyl group, 1-methylbutyl group, n-pentyl group, n-hexyl group; 2-hydroxyethyl group, 2-methoxyethyl group, 2-cyanoethyl group, trifluoro A substituted alkyl group such as a methyl group; From the viewpoint of obtaining a more preferable hue and ease of synthesis, the alkyl group preferably has 1 to 3 carbon atoms. Of these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are particularly preferable. In addition, a more preferable hue can be obtained, and from the viewpoint of ease of synthesis, the substituents in the case where R ₁ , R ₅ , R ₆ and R ₁₀ have a substituent may be of the same type. preferable.

The sulfonic acid groups of R ₁ , R ₅ , R ₆ and R ₁₀ , together with sulfonic acid groups and sulfamoyl groups that may exist other than this, impart water solubility to the compound represented by the general formula (1). . The sulfonic acid group may be either acid type or salt type. Examples of counter ions for forming a salt in the case of a salt type sulfonic acid group include alkali metals such as lithium, sodium, and potassium; unsubstituted ammonium; methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, and ethylammonium. Organic ammonium such as diethylammonium, triethylammonium, tetraethylammonium, n-propylammonium, isopropylammonium, diisopropylammonium, n-butylammonium, tetran-butylammonium, isobutylammonium, monoethanolammonium, diethanolammonium, triethanolammonium; Is mentioned. Note that not only the sulfonic acid groups of R ₁ , R ₅ , R ₆ and R ₁₀ but also other ionic groups which the compound represented by the general formula (1) may have, either acid type or salt type It may be. For example, as a counter ion in the case of a salt type ionic group, the same counter ions as those described above can be mentioned.

Examples of the halogen atom for R ₁ , R ₅ , R ₆ and R ₁₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In general formula (1), R ₂ , R ₄ , R ₇ and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group.

Examples of the alkyl group for R ₂ , R ₄ , R ₇ and R ₉ include the same alkyl groups as those for R ₁ , R ₅ , R ₆ and R ₁₀ .

Examples of the alkoxy group of R ₂ , R ₄ , R ₇ and R ₉ include linear or branched alkoxy groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. The alkoxy group of R ₂ , R ₄ , R ₇ and R ₉ may have a substituent as long as the hue and light resistance of the compound represented by the general formula (1) are not impaired. Examples of such a substituent include a hydroxy group; an alkoxy group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group; a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; Can be mentioned. Examples of the alkoxy group of R ₂ , R ₄ , R ₇ and R ₉ include those having a substituent, for example, an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group; 2 -Substituted alkoxy groups such as methoxyethoxy group, 2-hydroxyethoxy group, and 3-carboxypropoxy group;

Examples of the aryloxy group of R ₂ , R ₄ , R ₇ and R ₉ include aryloxy groups having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and particularly preferably 6 to 10 carbon atoms. The aryloxy group of R ₂ , R ₄ , R ₇ and R ₉ may have a substituent as long as the hue and light resistance of the compound represented by the general formula (1) are not impaired. Examples of such a substituent include a hydroxy group; an alkoxy group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group; a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; Can be mentioned. Examples of the aryloxy group of R ₃ and R ₈ include those having a substituent, for example, a phenoxy group, a 2-naphthoxy group, a 1-anthryloxy group, a 9-phenanthryloxy group, and a 1-azurenyloxy group. Unsubstituted aryloxy groups such as p-methoxyphenoxy group, o-methoxyphenoxy group, o-tolyloxy group, p-tolyloxy group, 2,3-xylyloxy group, 3,5-xylyloxy group, 4-carboxy-2-yl And substituted aryloxy groups such as methylphenoxy group and 4-sulfo-2-methylphenoxy group.

R ₂ , R ₄ , R ₇ and R ₉ are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group. Moreover, from the viewpoint of ease of synthesis, it is preferable that the substituents in the case where R ₂ , R ₄ , R ₇ and R ₉ have a substituent are all of the same type.

In General Formula (1), R ₃ and R ₈ each independently represent a hydrogen atom, an alkyl group, a sulfonic acid group, or a group represented by the following General Formula (2), and at least one of R ₃ and R ₈ The above is a group represented by the general formula (2). Although the compound represented by the general formula (1) of the present invention has a preferable hue in the magenta to blue region, C.I. I. Acid Red 52 and C.I. I. It has light resistance superior to Acid Red 289. For this purpose, it is important that at least one of R ₃ and R ₈ is a group represented by the general formula (2).

Examples of the alkyl group for R ₃ and R ₈ include the same alkyl groups as those for R ₁ , R ₅ , R ₆ and R ₁₀ .

The sulfonic acid group of R ₃ and R ₈ imparts solubility in water to the compound represented by the general formula (1) together with a sulfonic acid group and a sulfamoyl group that may exist in addition to the above. The sulfonic acid group of R ₃ and R ₈ may be either acid type or salt type, similarly to the sulfonic acid group of R ₁ , R ₅ , R ₆ and R ₁₀ . Examples of the counter ion that forms a salt in the case of a salt-type sulfonic acid group include those similar to the sulfonic acid groups of R ₁ , R ₅ , R _6, and R ₁₀ .

The group represented by the general formula (2) of R ₃ and R ₈ is an acylamino group to which R ₁₁ (an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or a heterocyclic group) is bonded. is there. R ₁₁ may have a substituent as long as the hue of the compound represented by the general formula (1) and the light resistance are not impaired. Examples of such a substituent include alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, n-propyl group, and isopropyl group; vinyl group, 1-propenyl group, 2-propenyl group, and 1-methylethenyl. Group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like alkenyl group having 2 to 4 carbon atoms; hydroxy group; methoxy group, ethoxy group, propoxy group and other alkoxy groups having 1 to 3 carbon atoms; phenyl An aryl group having 6 to 12 carbon atoms such as a group or a naphthyl group; an aralkyl group having 7 to 14 carbon atoms such as a benzyl group, a 2-phenethyl group or a naphthylethyl group; a cyano group; a methylamino group, an ethylamino group, n- C1-C3 alkylamino groups such as propylamino group and isopropylamino group; sulfomethyl group, sulfoethyl group, sulfon-pro A sulfoalkyl group having 1 to 3 carbon atoms such as a sulfur group and a sulfoisopropyl group; a carbamoyl group; a sulfamoyl group; a sulfonylamino group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a carboxylic acid group, a sulfonic acid group and a phosphorus And ionic groups such as acid groups and phosphonic acid groups.

Examples of the alkyl group for R ₁₁ include linear or branched alkyl groups having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. Examples of the alkyl group of R ₁₁ include those having a substituent, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group. 1-methylbutyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, sec-hexyl group, n-heptyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, sec-hexyl group, n-heptyl group, sec-heptyl group, n-octyl group, 2-ethylhexyl group, 2-ethylhexyl group, sec- Octyl group, n-nonyl group, sec-nonyl group, n-decyl group, sec-decyl group, n-undecyl Group, sec-undecyl group, n-dodecyl group, sec-dodecyl group, tridecyl group, isotridecyl group, sec-tridecyl group, tetradecyl group, sec-tetradecyl group, hexadecyl group, sec-hexadecyl group, n-stearyl group, 2 -No butyloctyl group, 2-butyldecyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-hexadecyl group, octadecyl group, etc. Substituted alkyl group; hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, 4-sulfobutyl group, hydroxyoctyl group, hydroxynonyl group, hydroxydecanyl group, 2-ethoxyhexyl group, 2-ethoxyheptyl group, 2-ethyl Kishiokuchiru group, a substituted alkyl group such as 1-ethoxy decahydronaphthyl group; and the like.

Examples of the cycloalkyl group represented by R ₁₁ include a monocyclic or multicyclic cycloalkyl group having 3 to 18 carbon atoms, preferably 5 to 12 carbon atoms. Examples of the cycloalkyl group represented by R ₁₁ include those having a substituent, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, bornyl group, isobornyl group, 1-norbornyl group, 1-norbornyl group, Bicyclo [2.2.2] octyl group, 1-adamantyl group, 3-noradamantyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cyclohepta Unsubstituted cycloalkyl groups such as decyl group and cyclooctadecyl group; 1-isopropylcyclohexyl group, 1-adamantylmethyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexane Xyl group, 3,5-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 1-isopropylcyclohexyl group, 2,6-diisopropylcyclohexyl group, 4-tert-butyl And unsubstituted cycloalkyl groups such as a cyclohexyl group and a 3-tert-butylcyclohexyl group.

Examples of the aryl group for R ₁₁ include monocyclic or multicyclic aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. As the aryl group of R ₁₂ , including those having a substituent, for example, an unsubstituted aryl group such as a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an azulenyl group; a p-methoxyphenyl group, o -Substituted aryl groups such as a chlorophenyl group, m- (3-sulfopropylamino) phenyl group, o-carboxyphenyl group;

Examples of the aralkyl group represented by R ₁₁ include aralkyl groups having 7 to 14 carbon atoms, preferably 7 to 10 carbon atoms. Examples of the aralkyl group for R ₁₁ include a benzyl group, a p-tolyl group, a xylyl group, a 2-phenethyl group, and a naphthylethyl group.

Examples of the alkenyl group for R ₁₁ include linear or branched alkenyl groups having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Examples of the alkenyl group for R ₁₁ include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylethenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.

As the heterocyclic group for R _11, a 5- or 6-membered heterocyclic group is preferable, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. In addition, the heterocycle may be condensed with an aliphatic ring, an aromatic ring, or another heterocycle. Examples of the heterocyclic group of R ₁₂ include imidazolyl group, benzoimidazolyl group, pyrazolyl group, benzopyrazolyl group, triazolyl group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzoisothiazolyl group, oxazolyl group, benzoxazolyl group , Thiadiazolyl group, pyrrolyl group, benzopyrrolyl group, indolyl group, isoxazolyl group, benzoisoxazolyl group, thienyl group, benzothienyl group, furyl group, benzofuryl group, pyridyl group, quinolyl group, isoquinolyl group, pyridazinyl group, pyrimidinyl group , Pyrazinyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, triazinyl group and the like.

R ₁₁ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group because a more preferable hue is obtained. Among these, a hydrogen atom, an alkyl group, or an aryl group is more preferable because better light resistance can be obtained.

From the viewpoint of ease of synthesis of the compound represented by the general formula (1), the following cases are preferable. When the compound represented by the general formula (1) has two or more groups represented by the general formula (2), it is preferable that the groups represented by the general formula (2) have the same structure. Moreover, it is preferable that both R ₃ and R ₈ are groups represented by the general formula (2). Each combination of _{R 1} and _R 6, _{R 2} and _R 7, _{R 3} and _R 8, _{R 4} and _R 9, _{R 5} and _{R 10} are preferably each the same group.

In general formula (1), Z represents a sulfonic acid group or a sulfamoyl group each independently. When at least one of R ₁ to R ₁₀ has an ionic group, n represents an integer of 0 to 6, and when R ₁ to R ₁₀ do not have an ionic group, n exceeds 0 and is 6 or less. Represents an integer. When Z is present, it is substituted at the position of at least one hydrogen atom of the aromatic ring in the general formula (1). Examples of ionic groups that R ₁ to R ₁₀ may have include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group.

The sulfonic acid group of Z gives water solubility to the compound represented by the general formula (1) together with other ionic groups and sulfamoyl groups that may be present. The sulfonic acid group may be either acid type or salt type. Examples of the counter ion that forms a salt in the case of a salt-type sulfonic acid group include those similar to those in the sulfonic acid group of R ₁ , R ₅ , R _6, and R ₁₀ .

  The sulfamoyl group of Z may have a substituent as long as the hue and light resistance of the compound represented by the general formula (1) are not impaired. Examples of such a substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group. Examples of the sulfamoyl group of Z include those having a substituent, for example, an unsubstituted sulfamoyl group (aminosulfonyl group); N-methylaminosulfonyl group, N, N-dimethylaminosulfonyl group, Nn-butyl. And a substituted sulfamoyl group substituted with an alkyl group having 1 to 4 carbon atoms such as an aminosulfonyl group.

n represents the number of substitutions of Z in the general formula (1). When at least one of R ₁ to R ₁₀ has an ionic group, n represents an integer of 0 to 6, and when R ₁ to R ₁₀ do not have an ionic group, n exceeds 0 and is 6 or less. Represents an integer. That is, when n = 0, the compound represented by the general formula (1) does not have a sulfonic acid group or sulfamoyl group as Z. In this case, in order to ensure the solubility of the compound as a dye in water, at least one of R ₁ to R ₁₀ needs to have an ionic group. On the other hand, when at least one of R ₁ to R ₁₀ has an ionic group, the compound can be dissolved in water by this ionic group, and therefore n = 0 may be sufficient.

  In order to further improve the solubility of the compound represented by the general formula (1) in water, n is preferably 1 or more. In addition, n is preferably 4 or less from the viewpoint of ease of purification after synthesis (such as salting out and aciding out). In addition, the compound represented by General formula (1) may be a mixture of a plurality of compounds having different numbers of n. In the present invention, in the case of a mixture, n is expressed with a width. When it is a mixture, the median compound of the range is usually the most abundant. For example, a compound represented by n = 2-4 is a mixture including compounds of n = 2, 3, and 4, and the ratio of the compound of n = 3 is the largest.

  Moreover, since the solubility to water can be improved more, it is preferable that the compound represented by General formula (1) has an ionic group. In this case, it is preferable that n in the general formula (1) is an integer of 1 to 3, and Z is a sulfonic acid group. In this case, the sulfonic acid group is in a salt form, and the counter ion of the sulfonic acid group is more preferably at least one selected from the group consisting of lithium ions, sodium ions, potassium ions, and ammonium ions.

The substitution position of Z in the main skeleton of the compound represented by the general formula (1) (that is, the structure in [] of the general formula (1)) is the substitution position of other substituents of the general formula (1), It is determined by the reaction conditions of sulfonation or chlorosulfonation. When all of R ₁ to R ₁₀ are substituents other than hydrogen atoms and R ₁₁ does not have an aromatic hydrogen atom, Z is substituted at the position of the hydrogen atom of the xanthene skeleton. Further, when at least one of R ₁ to R ₁₀ is a hydrogen atom, Z may be substituted at the position of the hydrogen atom. In addition, when R ₁₁ has an aromatic ring and an aromatic hydrogen atom, Z may be substituted with the aromatic ring in R ₁₁ . From the viewpoint of ease of synthesis, it is preferable that Z is substituted at the hydrogen atom position of the xanthene skeleton.

The compound represented by the general formula (1) has tautomers. As the tautomer, in addition to the compound represented by the general formula (1), compounds represented by the following general formulas (1a) and (1b) can be considered. In the present invention, these compounds (tautomers) and salts are also included in the compound represented by the general formula (1). In addition, R < ₁ > -R < ₁₀ > in general formula (1a) and (1b) is synonymous with R < ₁ > -R < ₁₀ > in the said general formula (1).

The compound represented by the general formula (1) can be synthesized based on a known method. An example of a synthesis scheme is shown below. Compound in Synthesis Scheme (B), (C), (D) _R 1 in and (E) _{to R} 10, Z, n is in the _R 1 _{to R} 10, Z, in n synonymous formula (1) is there. In addition, the compound represented by the general formula (1) can be synthesized as a mixture of a plurality of isomers having different types, the number, and positions of substituents. However, for convenience, in the present invention, including a mixture, Described as “compound”.

  In the synthesis scheme exemplified above, the compound represented by the general formula (1) in which n = 0 is obtained through the first condensation step shown in the first step and the second condensation step shown in the second step. Synthesize. In addition to this, when further increasing the solubility of the compound in water, a sulfonation or sulfamoylation step may be added as the third stage, in which case n = 1 to 6 The compound represented by (1) is obtained.

  First, in the first condensation step, compound (C) is obtained by condensing compound (A) and compound (B) by heating in the presence of an organic solvent or a condensing agent. Next, in the second condensation step, the compound (D) and the compound (C) obtained in the first condensation step are heated and condensed to give the compound (E) (n = 0 in general) A compound represented by the formula (1) is obtained. In order to further increase the solubility of the compound in water, the compound (E) obtained in the second condensation step can be sulfonated using a sulfonating agent such as concentrated sulfuric acid or fuming sulfuric acid. Thereby, a compound (F) in which Z is a sulfonic acid group (a compound represented by the general formula (1) where n = 1 to 6) is obtained. In addition, the compound (E) obtained in the second condensation step is chlorosulfonated using chlorosulfonic acid or the like, and then reacted with an amine compound such as concentrated aqueous ammonia, alkylamine or arylamine to be sulfamoylated. Thus, a compound (F) in which Z is a sulfamoyl group (a compound represented by the general formula (1) where n = 1 to 6) is obtained.

  The organic solvent used in the condensation reaction of the synthesis scheme exemplified above will be described. In the first condensation step, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol and the like are preferably used alone or in combination. In the second condensation step, for example, ethylene glycol, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, etc. are used alone or in combination. And preferably used.

  The reaction temperature in the first condensation step is preferably 60 ° C. to 100 ° C., more preferably 70 ° C. or more and 90 ° C. or less. The reaction temperature in the second condensation step is preferably 120 ° C to 220 ° C, and more preferably 180 ° C or lower.

When synthesizing a compound in which R _{1 to} R ₅ and R _{6 to} R ₁₀ in the general formula (1) are the same group, the same kind as the compound (B) and the compound (D) in the above synthesis scheme is used. Things can be used. Therefore, in this case, the compound represented by the general formula (1) can be obtained by performing a one-step condensation process from the compound (A). The reaction temperature at that time is preferably 120 ° C. to 220 ° C., more preferably 180 ° C. or less. As the condensing agent, for example, magnesium oxide, zinc chloride, aluminum chloride or the like can be used.

The compound which is the final product obtained by the above synthesis scheme is processed in accordance with a post-treatment method of a normal organic synthesis reaction and then purified, for example, for a desired use such as an ink coloring material (dye). Can be used. For identification of the compound represented by the general formula (1), ¹ H NMR analysis, LC / MS analysis, UV / Vis spectroscopic analysis and the like can be used.

  The compound represented by the general formula (1) of the present invention has high magenta color developability and is excellent in light resistance, moisture resistance and ozone resistance. The compound represented by the general formula (1) can be suitably used as a coloring material for various inks such as printing, painting, writing instruments, and ink jet. In addition to various inks, the compound represented by the general formula (1) can be suitably used as a color material applied to optical recording, color filters, and the like.

<Ink>
The ink of the present invention is a suitable ink for ink jetting containing the compound represented by the general formula (1) of the present invention described above as a color material (dye). The content (% by mass) of the compound represented by the general formula (1) in the ink is 0.10% by mass or more and 10.00% by mass or less, and further 0.20% by mass or more based on the total mass of the ink. It is preferable that it is 5.00 mass% or less.
Hereinafter, other components constituting the ink of the present invention will be described.

(Other color materials)
The present inventors use, as a coloring material, an ink containing a compound having a structure different from that of the general formula (1) in addition to the compound represented by the general formula (1). It was found that the light resistance was further improved without impairing the preferred hue of the compound represented by formula (1).

Examples of the compound (other colorant) having a structure different from that of the general formula (1) that can be used in addition to the compound represented by the general formula (1) include pigments and dyes. More preferably, it is used. As other color materials, materials of any hue classified into cyan, magenta, yellow, red, blue, green, black and the like may be used. In particular, it is preferable to use a dye having a hue of magenta to red, and it is more preferable to use a dye such as a compound having an azo skeleton or an anthrapyridone skeleton. More specifically, from the viewpoint of obtaining a more preferable hue, a compound having a maximum absorption wavelength (λ _max ) in water of 380 to 590 nm, particularly 480 to 570 nm, particularly 500 to 560 nm is used. preferable.

  Examples of the compound having an azo skeleton include C.I. I. Acid Red 249, and those described in JP-A No. 08-073791, JP-A No. 2002-371214, JP-A No. 2006-143898, and the like. Specific examples include compounds represented by the following general formula (I) and compounds represented by the following general formula (II). Moreover, the following are mentioned as a compound which has an anthrapyridone skeleton. For example, monomer structures described in International Publication No. 1998/011167, International Publication No. 1998/011167, International Publication No. 2004/104108, International Publication No. 2009/060654, International Publication No. 2009/093433, and the like. And so on. Moreover, the thing of the dimer structure described in international publication 2003/027185, international publication 2006/0775706, international publication 2008/066062, Unexamined-Japanese-Patent No. 2010-006969 etc. is mentioned. Specific examples include compounds represented by the following general formula (III), compounds represented by the following general formula (IV), and the like. Of course, the present invention is not limited to the following compounds.

(In the general formula (I), R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a carboxy group, a hydroxy group, a sulfonic acid group, or an alkyl group. M independently represents a hydrogen atom. Represents an atom, alkali metal, ammonium, or organic ammonium)

(In the general formula (II), R _{1 to} R ₈ each independently represents a hydrogen atom, a halogen atom, a cyano group, a carboxy group, a hydroxy group, a sulfonic acid group, or an alkyl group. M independently represents a hydrogen atom. Represents an atom, alkali metal, ammonium, or organic ammonium)

(In general formula (III), R ₁ represents an alkylcarbonyl group, an alkoxycarbonyl group, an arylcarbonyl group, or an aryloxycarbonyl group. R ₂ represents a hydrogen atom or an alkyl group. R ₃ represents an anilino. Represents a group.)

(In general formula (IV), R ₁ represents an alkylcarbonyl group, an alkoxycarbonyl group, an arylcarbonyl group, or an aryloxycarbonyl group. R ₂ represents a hydrogen atom or an alkyl group. R ₃ represents an anilino. R ₄ represents a linking group, and each M independently represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)
Specific examples of the compound having an azo skeleton include azo compounds 1 to 4 having the following structure in the form of a free acid. Specific examples of the compound having an anthrapyridone skeleton include anthrapyridone compounds 1 to 9 having the following structure in the form of a free acid. Of course, the present invention is not limited to the following compounds.

  When a compound having a structure different from the general formula (1) is used as the color material of the ink, the content (% by mass) of the compound in the ink is 0.10% by mass or more based on the total mass of the ink. It is preferable that it is 10.00 mass% or less. Furthermore, it is more preferable that it is 0.30 mass% or more and 5.00 mass% or less. Further, in the case where a compound having a structure different from that of the general formula (1) is used as the ink coloring material in addition to the compound represented by the general formula (1), the content of each compound is as follows. It is preferable to make it. That is, in order to obtain a more preferable hue, the content (% by mass) of the compound represented by the general formula (1) in the ink is preferably 0.35% by mass or more based on the total mass of the ink. In this case, the upper limit of the content (% by mass) of the compound represented by the general formula (1) in the ink is 10.00% by mass or less, and further 5.00, as in the case described above. It is preferable that it is below mass%. The total content (% by mass) of each compound (coloring material) in the ink is preferably 0.10% by mass or more and 10.00% by mass or less based on the total mass of the ink.

  The inventors of the present invention include a compound represented by the general formula (1) and a compound having a structure different from the general formula (1) in a specific mass ratio, while maintaining a more preferable hue. The knowledge that light resistance can be further improved was obtained. Specifically, the content (mass%) of the compound represented by the general formula (1) based on the total mass of the ink has a structure (mass%) having a structure different from that of the general formula (1). %), The mass ratio is preferably 0.50 times or more and 9.00 times or less. The mass ratio is more preferably 0.50 times or more and 1.00 times or less.

(Aqueous medium)
In the ink of the present invention, water or an aqueous medium that is a mixed solvent of water and a water-soluble organic solvent can be used. It is preferable to use deionized water (ion exchange water) as the water. The content (% by mass) of water in the ink is preferably 10.0% by mass or more and 90.0% by mass or less based on the total mass of the ink. The ink of the present invention is preferably an aqueous ink containing at least water as an aqueous medium.

  The water-soluble organic solvent is not particularly limited as long as it is water-soluble, and monovalent or polyhydric alcohols, alkylene glycols, glycol ethers, nitrogen-containing polar compounds, sulfur-containing polar compounds, and the like can be used. . The content (% by mass) of the water-soluble organic solvent in the ink is 5.0% by mass or more and 90.0% by mass or less, and further 10.0% by mass or more and 50.0% by mass or less based on the total mass of the ink. It is preferable that When used as an inkjet ink, if the content of the water-soluble organic solvent is within the above range, the ejection stability from the recording head can be sufficiently satisfied.

(Other additives)
In addition to the components described above, the ink of the present invention is a water-soluble organic substance that is solid at room temperature, such as polyhydric alcohols such as trimethylolpropane and trimethylolethane, and urea derivatives such as urea and ethyleneurea, if necessary. A compound may be contained. Furthermore, the ink of the present invention includes a surfactant, a pH adjuster, an antiseptic, an antifungal agent, an antioxidant, an anti-reduction agent, an evaporation accelerator, a chelating agent, and a water-soluble resin, if necessary. Various additives may be contained.

<Ink cartridge>
The ink cartridge of the present invention includes ink and an ink storage unit that stores the ink. And the ink accommodated in this ink accommodating part is the ink of this invention demonstrated above.

<Inkjet recording method>
The ink jet recording method of the present invention is a method of recording an image on a recording medium by discharging the ink of the present invention described above from an ink jet recording head. Examples of the method for ejecting ink include a method for imparting mechanical energy to the ink and a method for imparting thermal energy to the ink. In the present invention, it is particularly preferable to employ a system in which thermal energy is applied to the ink and ink is ejected. Other than using the ink of the present invention, the steps of the ink jet recording method may be known.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited by the following Example, unless the summary is exceeded. In addition, what is described as “parts” and “%” with respect to the component amounts is based on mass unless otherwise specified.

<Synthesis of Compound Represented by General Formula (1)>
(Exemplary Compound 1)
4-isobutyrylamino-2,3,5,6-tetramethylaniline (8.9 g) and compound (A) (7.4 g) in the above synthesis scheme were combined with zinc chloride (20 mL) in zinc chloride (20 mL). In the presence of 4.1 g), the reaction was carried out by heating at a temperature of 150 ° C. for 3 hours. After cooling this solution, it was added to 50 mL of 2 mol / L hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and then dried to obtain a dried product. 6 g of the obtained dried product was added to 30 g of fuming sulfuric acid under ice cooling, and then stirred at a temperature of 20 to 25 ° C. for 4 hours. The reaction solution was discharged onto 100 g of ice, and the precipitated solid was collected by filtration and then washed with cold water to obtain a precipitate. The obtained precipitate was suspended in 50 mL of water, dissolved in 2 mol / L sodium hydroxide aqueous solution to pH 7.0, crystallized with acetone, and exemplified compound 1 represented by the following structural formula Got.

(Other compounds)
Each compound shown in Tables 1 and 2 was synthesized according to the synthesis method of the exemplified compound 1 described above. Tables 1 and 2 also show the structure of Example Compound 1 synthesized earlier. In Tables 1 and 2, “Me” represents methyl, and “Ph” represents phenyl. “*” Represents a binding site of the substituent.

<Preparation of ink>
Each component (unit:%) shown below was mixed and sufficiently stirred to dissolve, and then pressure filtration was performed using a filter having a pore size of 0.2 μm to prepare each ink. Acetylenol E100 is a nonionic surfactant manufactured by Kawaken Fine Chemicals. Tables 3 to 5 show the content C ₁ (%) of the compound represented by the general formula (1) and the content C ₂ (%) of a compound having a structure different from that of the general formula (1). . Moreover, the value of the mass ratio (times) of “content C ₁ of the compound represented by the general formula (1) / content C ₂ of a compound having a structure different from the general formula (1)” is also shown.
Color materials (types shown in Tables 3 to 5): Amounts used (%) shown in Tables 3 to 5
・ Ethylene glycol: 9.00%
・ Diethylene glycol: 9.00%
-Acetinol E100: 1.00%
・ Ion-exchanged water: remaining amount that totals 100.00%

In addition, the azo compounds 1 and 2 which have the above-mentioned structure were used as lithium salt. Azo compounds 3 and 4 and anthrapyridone compounds 1-9 were used as sodium salts. As a comparative compound, a compound having the following structure in the form of a free acid was used as a sodium salt.
Comparative compound 1: C.I. I. Acid Red 289
Comparative compound 2: C.I. I. Acid Red 52
Comparative compound 3: Dye I-12 of Patent Document 1
Comparative Compound 4: Dye Comparative Compound 6 of Example 3 of Patent Document 2: Exemplary Compound 1 of Patent Document 3
Comparative compound 5: Exemplified compound I-8 of Patent Document 4
Comparative compound 7: Dye compound (8) of Patent Document 5
Comparative Compound 8: Dye (1A) of Patent Document 6
Comparative compound 9: Compound (2A) of Patent Document 7

<Evaluation>
Each of the inks obtained above was filled in an ink cartridge and mounted on an ink jet recording apparatus (PIXUS iP8600; manufactured by Canon) that ejects ink from the recording head by the action of thermal energy. In this embodiment, a solid image recorded by applying 8 ink droplets of 2.5 pL per droplet to a unit area of 1/600 inch × 1/600 inch is recorded as “recording duty is 100%”. Define. Using this inkjet recording device, the recording duty is 10% to 100% on glossy paper (Canon Photo Paper / Glossy Pro [Platinum Grade] PT-201; manufactured by Canon) in an environment of 23 ° C. and 55% relative humidity. 10 types of solid images, each of which was changed in 10% increments, were recorded to obtain a recorded matter. The obtained recorded matter was dried for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 55%. The following evaluation was performed using this recorded matter. The color of the image was measured using a spectrophotometer (trade name “Spectorolino”, manufactured by Gretag Macbeth) under the conditions of light source: D50 and field of view: 2 °. ^{Incidentally,} L *, ^{a *} and ^{b *} is, ^L * in ^{the L} * ^a * ^{b *} display system defined by the CIE (Commission Internationale de l'Eclairage), is ^{a *} and ^{b *.}

(saturation)
Measure a ^* and b ^* for a solid image portion having a recording duty of 50% in a recorded matter, and calculate a value of saturation C ^* = {(a ^* ) ² + (b ^* ) ² } ^1/2 did. From the obtained C ^* value, the saturation was evaluated according to the following evaluation criteria. In the present invention, a case where the evaluation result is A is an acceptable level, and a case where the evaluation result is B is an unacceptable level. The evaluation results shown in Tables 6 and 7 were: A: C ^* was 80 or more B: C ^* was less than 80.

(Hue angle)
A ^* and b ^* were measured for the solid image portion of each recording duty in the recorded matter. Then, a solid image having an a ^* closest to 50 among 10 types of solid images was identified, and the value of the hue angle H ° was calculated from the values of a ^* and b ^* of the solid image based on the following equation.
When a ^* ≧ 0 and b ^* ≧ 0 (first quadrant), the hue angle H ° = tan ⁻¹ (b ^* / a ^* )
When a ^* ≦ 0 and b ^* ≧ 0 (second quadrant), the hue angle H ° = 180 + tan ⁻¹ (b ^* / a ^* )
When a ^* ≦ 0 and b ^* ≦ 0 (third quadrant), the hue angle H ° = 180 + tan ⁻¹ (b ^* / a ^* )
In the case of a ^* ≧ 0 and b ^* ≦ 0 (fourth quadrant), the hue angle H ° = 360 + tan ⁻¹ (b ^* / a ^* ).

From the obtained H ° value, the hue angle was evaluated according to the following evaluation criteria. In the present invention, a case where the evaluation result is A is an acceptable level, and a case where the evaluation result is B is an unacceptable level. The evaluation results are shown in Tables 6 and 7.
A: H ° was 300 ° or more and less than 340 ° B: H ° was 0 ° or more and less than 300 °, or 340 ° or more and less than 360 °.

(Light resistance)
The optical density of a solid image having a recording duty of 50% on the recorded matter was measured (referred to as “optical density before test”). Thereafter, this recorded matter was put in a xenon test apparatus (xenon weather meter SX-75; manufactured by Suga Test Instruments Co., Ltd.) for 240 hours (condition 1) under conditions of a bath temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 50 klx. The solid image was irradiated with xenon light for 360 hours (condition 2). Next, the optical density of the solid image having a recording duty of 50% in the recorded matter was measured (referred to as “optical density after test”). Then, the residual ratio of optical density (%) = (optical density after test / optical density before test) × 100 was calculated, and light resistance (conditions 1 and 2) was evaluated according to the evaluation criteria shown below.

[Evaluation criteria for condition 1]
A: The residual ratio of the optical density was 85% or more. B: The residual ratio of the optical density was less than 85%. In the present invention, an acceptable level when the evaluation result in the condition 1 is A is B. Some cases were considered unacceptable levels. The evaluation results are shown in Tables 6 and 7.

[Evaluation criteria for condition 2]
AA: The residual ratio of optical density was 90% or more A: The residual ratio of optical density was 85% or more and less than 90% B: The residual ratio of optical density was 75% or more and less than 85% C: The residual ratio of optical density was less than 75%. Condition 2 is for evaluating the light resistance of an image under more severe conditions than Condition 1, and is superior to C, B, A, and AA in this order. It means having light resistance. The evaluation results are shown in Tables 6 and 7.

  The evaluation results of “saturation” in Examples 43 and 44 were both “A”, but Example 43 was relatively superior to Example 44.

Claims (6)

A compound represented by the following general formula (1).

(In General Formula (1), R ₁ , R ₅ , R ₆ and R ₁₀ each independently represents an alkyl group, a sulfonic acid group, or a halogen atom. R ₂ , R ₄ , R ₇ and R ₉ are each Independently represents a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and R ₃ and R ₈ are each independently represented by a hydrogen atom, an alkyl group, a sulfonic acid group, or the following general formula (2). And at least one of R ₃ and R ₈ is a group represented by the following general formula (2): Z independently represents a sulfonic acid group or a sulfamoyl group, and R ₁ to R ₁₀ When at least one has an ionic group, n represents an integer of 0 to 6, and when R ₁ to R ₁₀ do not have an ionic group, n represents an integer of more than 0 and 6 or less, Z In the general formula (1) Substituted at the position of at least one of the hydrogen atoms of incense ring.)

(In the general formula (2), R ₁₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or a heterocyclic group. * Represents a bonding site with the aromatic ring of the general formula (1). Represents.) An ink containing a coloring material,
The ink characterized in that the color material contains a compound represented by the following general formula (1).

(In General Formula (1), R ₁ , R ₅ , R ₆ and R ₁₀ each independently represents an alkyl group, a sulfonic acid group, or a halogen atom. R ₂ , R ₄ , R ₇ and R ₉ are each Independently represents a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and R ₃ and R ₈ are each independently represented by a hydrogen atom, an alkyl group, a sulfonic acid group, or the following general formula (2). And at least one of R ₃ and R ₈ is a group represented by the following general formula (2): Z independently represents a sulfonic acid group or a sulfamoyl group, and R ₁ to R ₁₀ When at least one has an ionic group, n represents an integer of 0 to 6, and when R ₁ to R ₁₀ do not have an ionic group, n represents an integer of more than 0 and 6 or less, Z In the general formula (1) Substituted at the position of at least one of the hydrogen atoms of incense ring.)

(In the general formula (2), R ₁₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or a heterocyclic group. * Represents a bonding site with the aromatic ring of the general formula (1). Represents.)   The ink according to claim 2, wherein the coloring material further contains a compound having a structure different from that of the general formula (1).   The ink according to claim 2 or 3, which is for inkjet. An ink cartridge comprising ink and an ink containing portion for containing the ink,
An ink cartridge, wherein the ink is the ink according to any one of claims 2 to 4. An inkjet recording method for recording an image on a recording medium by discharging ink from an inkjet recording head,
An ink jet recording method, wherein the ink is the ink according to any one of claims 2 to 4.