JP5264066B2 - Dye, ink composition containing dye, inkjet ink composition, and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment for color correction excellent in coloring, fixing, fastness and black tone. <P>SOLUTION: The pigment is represented by the general formula (I) satisfying one or both of the conditions. Condition 1: R<SB>1</SB>and R<SB>1</SB>' are H, an ionic hydrophilic group and a substituent having no OH group. Condition 2: the absolute value of the difference between &lambda;max (DMF) and &lambda;max (water) is 50 nm or less. In the formula, Ar<SB>1</SB>and Ar<SB>1</SB>' each represents a univalent aromatic hydrocarbon ring, Ar<SB>2</SB>, Ar<SB>2</SB>', Ar<SB>3</SB>and Ar<SB>3</SB>' each represents a bivalent aromatic carbon ring joining group, wherein at least one of Ar<SB>1</SB>to Ar<SB>3</SB>and Ar<SB>1</SB>' to Ar<SB>3</SB>' represents a naphthalene ring. A represents a substituent shown by the general formulae (II) to (IV) or a bivalent or over joining group shown by the general formula (V), R<SB>1</SB>, R<SB>1</SB>', R<SB>2</SB>and R<SB>3</SB>represent a hydrogen atom or a substituent, Q represents a bivalent or over joining group and q represents an integer of 2 or more. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a black ink composition (preferably a black ink composition for image formation (preferably an inkjet ink composition)) containing an azo dye having a specific structure and characteristics, and an inkjet recording method using the black ink composition. .

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force.
As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.

  For such colorants used in ink jet recording inks, they have good solubility or dispersibility in solvents, excellent color development, high density recording, good hue, light It is robust against active gases in the environment of heat, oxidizing gases such as NOx and ozone, SOx, etc., has excellent fastness to water and chemicals, and has fixability to image receiving materials. It is required that the ink does not bleed well, has excellent storability as an ink, has no toxicity, has high purity, and can be obtained at low cost. However, it is extremely difficult to search for colorants that meet these requirements at a high level. In particular, there is a strong demand for a colorant for black ink that has a good black tone, enables high-density printing, and is robust against light, humidity, and heat.

Conventionally, disazo dyes or trisazo dyes have been used as black pigments, but these dyes alone often lack blue to green light absorption and often do not provide a good black tone. In general, a dye for color correction that absorbs blue to green light is used in combination. As such a correction dye, for example, dyes as described in Patent Document 1 and Patent Document 2 have been proposed, and black tone adjustment ability, color developability, fastness, ink storage stability, water resistance, nozzle resistance, and the like. Improvements such as clogging have been attempted.
However, the conventionally proposed color correction dyes have a problem of lack of black tone adjustment ability, such as the necessity of adding a large amount because the absorption is too short, and the need for another color correction dye. I had it.

  Dyes that can absorb blue to green light are generally known, but their fastness is inferior, so the hue changes greatly upon exposure to light, heat, and active gases in the environment, and the fixability is insufficient. For this reason, almost all of the phenomena such as yellowing of the outline portion under high humidity conditions occur, and further improvement is necessary.

In view of these drawbacks, Patent Document 3 describes a black ink composition comprising a triazine dye having a maximum absorption spectrum of 435 nm in an aqueous solvent as a color correction dye, and a black dye. .
Further, Patent Documents 4 and 5 propose that a substituent such as an ionic hydrophilic group is introduced into the dye mother nucleus and the triazine ring in order to increase water solubility.
However, a general black dye has a maximum absorption of 570 to 620 nm, and even when the color correction dye is used, a suitable black tone cannot be obtained in consideration of a complementary color relationship important for black tone adjustment. This is clear (Non-Patent Document 1).
Based on this, Patent Document 6 proposes that a suitable black tone can be obtained by containing a dye whose absorption maximum in the visible absorption spectrum in a water solvent is 440 to 540 nm as a color correction dye. Yes.
However, the compound examples described in the patent document have problems such as lack of storage stability as ink, or color change (short wavelength) under high humidity and high temperature after printing on ink jet paper. It is hard to say that it still has sufficient performance.
JP-A-9-255906 Japanese Patent No. 3178200 JP 2002-332426 A JP 2005-298636 A International Publication No. 2006-001274 Pamphlet JP 2005-344071 A "Color Science Handbook (2nd edition)", The University of Tokyo Press, 1998, p560-562

An object of the present invention is to solve the above problems and achieve the following objects.
That is, an object of the present invention is to enable excellent black tone and high density printing without adding a large amount or other color correction dye, and color correction excellent in color development, fixing property and fastness. It is to provide a pigment. The present invention also provides a printing ink composition using such a color correction pigment and a water-based ink composition for writing.
Furthermore, an object of the present invention is to form an image having high color stability, ensuring good solution stability, having a good color tone for black, capable of high-density printing, and light and ozone. It is an object of the present invention to provide an inkjet recording ink composition having sufficient moisture and heat resistance that does not cause bleeding or color change even when stored at high humidity and high temperature, and an inkjet recording method using the inkjet recording ink composition. .

  The present inventors have aimed for a color correction dye having sufficient solution stability and good black tone control ability, good color development, high fastness to light and ozone, and excellent moisture and heat resistance. When various dye compounds were examined in detail, it was found that the above problems could be solved by the dyes having the specific structure and absorption characteristics described below.

一般式（ＶＩＩ）中、Ｒ _４ 、Ｒ _４ ’、Ｒ _５ 、Ｒ _５ ’、Ｒ _６ およびＲ _６ ’は、水素原子を表す。Ｌ _１ 、Ｌ _１ ’、Ｌ _２ およびＬ _２ ’は、夫々独立して、イオン性親水性基を示し、ｍ、ｍ’、ｎおよびｎ’は１〜２の整数を表す。Ａは、下記一般式（ＩＩ）で表される置換基、もしくは一般式（Ｖ）で表される連結基を表し、

一般式（ＩＩ）中、Ｒ _１ 、およびＲ _１ ’は、夫々独立して、水素原子、アルキル基またはシクロヘキシル基を表し、一般式（Ｖ）中、Ｑは下記一般式（ＸＸ）〜（ＸＸＶ）で表される２価〜３価の連結基を表し、ｑは２または３を表す。一般式（ＶＩ）中、Ｘはハロゲン原子を表す。

ただし、Ｒ _１ とＲ _１ ’とは互いに結合して５員環もしくは６員環を形成してもよく、前記アルキル基、シクロヘキシル基、５員環および６員環は、更にヒドロキシル基、アルコキシ基、カルボキシル基、スルホ基、アリール基、アリールオキシ基、アシル基、アシルオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、アミド基、カルバモイル基、スルホニル基、スルフィニル基、スルホンアミド基、スルファモイル基、シアノ基およびニトロ基を有していてもよい。また、Ｒ _１ およびＲ _１ ’は同時に２-ヒドロキシエチル基になることはなく、またＲ _１ が水素原子のときにＲ _１ ’が２-ヒドロキシエチル基、２-スルホエチル基およびスルホニルアリール基になることはない。
〔２〕
一般式（ＶＩＩ）が、下記一般式（ＶＩＩＩ）で表されることを特徴とする〔１〕に記載の色素。

一般式（ＶＩＩＩ）中、Ｍは、水素原子、金属カチオン、または有機カチオンを表す。Ａは、下記一般式（ＩＩ）で表される置換基、もしくは一般式（Ｖ）で表される連結基を表し、

一般式（ＩＩ）中、Ｒ _１ 、およびＲ _１ ’は、夫々独立して、水素原子、アルキル基またはシクロヘキシル基を表し、一般式（Ｖ）中、Ｑは下記一般式（ＸＸ）〜（ＸＸＶ）で表される２価〜３価の連結基を表し、ｑは２または３を表す。一般式（ＶＩ）中、Ｘはハロゲン原子を表す。

ただし、Ｒ _１ とＲ _１ ’とは互いに結合して５員環または６員環を形成してもよく、前記アルキル基、シクロヘキシル基、５員環および６員環は、更にヒドロキシル基、アルコキシ基、カルボキシル基、スルホ基、アリール基、アリールオキシ基、アシル基、アシルオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、アミド基、カルバモイル基、スルホニル基、スルフィニル基、スルホンアミド基、スルファモイル基、シアノ基およびニトロ基を有していてもよい。また、Ｒ _１ およびＲ _１ ’は同時に２-ヒドロキシエチル基になることはなく、またＲ _１ が水素原子のときにＲ _１ ’が２-ヒドロキシエチル基、２-スルホエチル基およびスルホニルアリール基になることはない。
〔３〕
〔１〕または〔２〕に記載の色素を少なくとも１種以上含有することを特徴とするインク組成物。
〔４〕
インクジェット用であることを特徴とする〔３〕のインク組成物。
〔５〕
〔１〕または〔２〕に記載の色素を少なくとも１種含有し、且つ該色素より長波長側に吸収極大を有する色素を含むことを特徴とする、インク組成物。
〔６〕
長波長側に吸収極大を有する色素が、下記一般式（ＩＸ）、（Ｘ）、（ＸＩ）および（ＸＩＩ）で表される色素のうち少なくとも１つの色素であることを特徴とする〔５〕に記載のインク組成物。

一般式（ＩＸ）中、Ａｒ _４ は、スルホ基によって置換されてもよい１価の芳香族基を表す。Ｒ _７ は、芳香族基（ただしフェニル基を除く）を表す。Ｙは、−ＣＨ＝または窒素原子を表す。Ｂ _１ およびＢ _２ は、それぞれ＝ＣＲ _１０ −および−ＣＲ _１１ ＝を表すか、あるいはいずれか一方が窒素原子，他方が＝ＣＲ _１０ −または−ＣＲ _１１ ＝を表す。Ｒ _１０ およびＲ _１１ は、それぞれ独立に、水素原子、メチル基またはシアノ基を表す。Ｇは、スルホ基によって置換されてもよいアリールアミノ基を表し、Ｒ _８ 、およびＲ _８ ’は、それぞれ独立に水素原子またはスルホ基によって置換されてもよいアリール基を表す。

一般式（Ｘ）中、Ａｒ _５ は、ニトロ基およびスルホ基によって置換されてもよい芳香族基を表し、Ａｒ _６ は、スルホ基、またはスルホ基およびヒドロキシル基によって置換されてもよい芳香族基を表し、Ａｒ _７ は、ニトロ基およびスルホ基によって置換されてもよい芳香族基、またはスルホ基、オキソ基およびアリール基によって置換されてもよい複素環基を表し、前記アリール基はさらにルホ基によって置換されていてもよい。Ｚはヒドロキシ基もしくはアミノ基のどちらかを表す。

一般式（ＸＩ）中、Ａｒ _８ は、アルコキシ基およびスルホ基によって置換されてもよい芳香族基を表し、Ａｒ _９ は、スルホ基によって置換されてもよい芳香族基を表す。ａおよびｂは、それぞれ単結合を表し、結合ａの結合位置は２位または３位であり、結合ｂの結合位置は６位または７位である。ｍ１およびｍ３は、それぞれ独立に０または１を表し、ｍ２は１および２を表す。）

一般式（ＸＩＩ）中、Ａｒ _１０ は、スルホ基によって置換されてもよい芳香族基 を表す。Ｒ _１２ は、水素原子またはアリール基を表し、Ｒ _１３ は、水素原子またはスルホ基によって置換されてもよいアルコキシ基を表し、Ｒ _１４ は、それぞれ独立に水素原子またはアルキル基を表す。ｃおよびｄは、それぞれ単結合を表し、結合ｃの結合位置は１０位または１１位であり、結合ｄの結合位置は１４位または１５位である。ｎ１およびｎ２は、それぞれ独立に０または１を表し、ｎ３は１および２を表す。）
なお、上記一般式（ＩＸ）〜（ＸＩＩ）で表される色素は、それぞれ塩の状態であってもよく、また任意の金属と錯体を形成していてもよい。
〔７〕
〔５〕および〔６〕に記載のインク組成物を用いたことを特徴とするインクジェット用インク組成物。
〔８〕
〔３〕〜〔７〕のいずれかに記載のインク組成物を少なくとも一種含むことを特徴とするインクセット。
〔９〕
〔３〕〜〔７〕のいずれかに記載のインク組成物を用いることを特徴とするインクジェット記録方法。
〔１０〕
支持体上に白色無機顔料粒子を含有するインク受容層を有する受像材料上に、〔３〕〜〔７〕に記載のインク組成物を用いて画像形成することを特徴とする〔９〕に記載のインクジェット記録方法。
〔１１〕
〔９〕および〔１０〕に記載の方法で画像形成したことを特徴とする着色体。
〔１２〕
〔３〕〜〔７〕に記載のインク組成物を含むことを特徴とする、インクジェットプリンターカートリッジ。
〔１３〕
〔１２〕に記載のインクジェットプリンターカートリッジを装填したことを特徴とするインクジェットプリンター。
なお、本発明は上記〔１〕〜〔１３〕に関するものであるが、その他の事項についても参考のために記載した。
（１） 下記一般式(Ｉ)で表される色素において、該色素が下記の条件のいずれか一方または両方を満たすことを特徴とする色素。
条件１：Ｒ_１およびＲ_１’が、水素原子、またはイオン性親水性基およびヒドロキシ基を持たない置換基である。
条件２：λmax（ＤＭＦ）とλmax（水）の差の絶対値が５０ｎｍ以下である。
λｍａｘ（ＤＭＦ）とλｍａｘ（水）は次のように定義する。即ち、ＤＭＦ：水＝９８：２で２５℃、０．００２％に調製された溶液を厚さ１０ｍｍのセルに入れ、分光光度計で測定した吸収スペクトルの可視領域における、最大吸収波長をλｍａｘ（ＤＭＦ）とし、同様に水溶媒中、で測定した吸収スペクトルの最大吸収波長をλｍａｘ（水）とする。 The present invention relates to the following [1] to [13].
[1]
A dye represented by the following general formula (VII):

In general formula (VII), R ₄ , R ₄ ′, R ₅ , R ₅ ′, R ₆ and R ₆ ′ represent a hydrogen atom. L ₁ , L ₁ ′, L ₂ and L ₂ ′ each independently represent an ionic hydrophilic group, and m, m ′, n and n ′ represent an integer of 1 to 2. A represents a substituent represented by the following general formula (II) or a linking group represented by the general formula (V),

In general formula (II), R ₁ and R ₁ ′ each independently represent a hydrogen atom, an alkyl group, or a cyclohexyl group, and in general formula (V), Q represents the following general formulas (XX) to (XXV) ) Represents a divalent to trivalent linking group, and q represents 2 or 3. In general formula (VI), X represents a halogen atom.

However, R ₁ and R ₁ ′ may be bonded to each other to form a 5-membered ring or a 6-membered ring. The alkyl group, cyclohexyl group, 5-membered ring and 6-membered ring are further a hydroxyl group, an alkoxy group. , Carboxyl group, sulfo group, aryl group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, amide group, carbamoyl group, sulfonyl group, sulfinyl group, sulfonamide group, sulfamoyl group , May have a cyano group and a nitro group. Also, R ₁ and R ₁ ′ are not simultaneously 2-hydroxyethyl groups, and when R ₁ is a hydrogen atom, R ₁ ′ is a 2-hydroxyethyl group, a 2-sulfoethyl group, and a sulfonylaryl group. There is nothing.
[2]
The dye according to [1], wherein the general formula (VII) is represented by the following general formula (VIII).

In general formula (VIII), M represents a hydrogen atom, a metal cation, or an organic cation. A represents a substituent represented by the following general formula (II) or a linking group represented by the general formula (V),

In general formula (II), R ₁ and R ₁ ′ each independently represent a hydrogen atom, an alkyl group, or a cyclohexyl group, and in general formula (V), Q represents the following general formulas (XX) to (XXV) ) Represents a divalent to trivalent linking group, and q represents 2 or 3. In general formula (VI), X represents a halogen atom.

However, R ₁ and R ₁ ′ may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the alkyl group, cyclohexyl group, 5-membered ring and 6-membered ring are further a hydroxyl group, an alkoxy group , Carboxyl group, sulfo group, aryl group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, amide group, carbamoyl group, sulfonyl group, sulfinyl group, sulfonamide group, sulfamoyl group , May have a cyano group and a nitro group. Also, R ₁ and R ₁ ′ are not simultaneously 2-hydroxyethyl groups, and when R ₁ is a hydrogen atom, R ₁ ′ is a 2-hydroxyethyl group, a 2-sulfoethyl group, and a sulfonylaryl group. There is nothing.
[3]
An ink composition comprising at least one pigment according to [1] or [2].
[4]
[3] The ink composition according to [3], which is for inkjet.
[5]
An ink composition comprising at least one dye according to [1] or [2] and having a dye having an absorption maximum on a longer wavelength side than the dye.
[6]
The dye having an absorption maximum on the long wavelength side is at least one of the dyes represented by the following general formulas (IX), (X), (XI) and (XII) [5] The ink composition described in 1.

In General Formula (IX), Ar ₄ represents a monovalent aromatic group that may be substituted with a sulfo group. R ₇ represents an aromatic group (excluding a phenyl group). Y represents —CH═ or a nitrogen atom. B ₁ and B ₂ each represent = CR ₁₀ -and -CR ₁₁ =, or either one represents a nitrogen atom and the other represents = CR ₁₀ -or -CR ₁₁ =. R ₁₀ and R ₁₁ each independently represents a hydrogen atom, a methyl group or a cyano group. G represents an aryl amino group which may be substituted by a sulfo group, R _8, and R _{8 'each} independently represent a hydrogen atom or a sulfo aryl group which may be substituted by group.

In general formula (X), Ar ₅ represents an aromatic group that may be substituted with a nitro group and a sulfo group, and Ar ₆ is an aromatic group that may be substituted with a sulfo group or a sulfo group and a hydroxyl group. Ar ₇ represents an aromatic group which may be substituted by a nitro group and a sulfo group, or a heterocyclic group which may be substituted by a sulfo group, an oxo group and an aryl group, and the aryl group is further a rupho group May be substituted. Z represents either a hydroxy group or an amino group.

In General Formula (XI), Ar ₈ represents an aromatic group that may be substituted with an alkoxy group and a sulfo group, and Ar ₉ represents an aromatic group that may be substituted with a sulfo group. a and b each represent a single bond, the bond position of the bond a is the 2nd or 3rd position, and the bond position of the bond b is the 6th or 7th position. m1 and m3 each independently represent 0 or 1, and m2 represents 1 and 2. )

In General Formula (XII), Ar ₁₀ represents an aromatic group that may be substituted with a sulfo group. R ₁₂ represents a hydrogen atom or an aryl group, R ₁₃ represents an alkoxy group which may be substituted with a hydrogen atom or a sulfo group, and R ₁₄ each independently represents a hydrogen atom or an alkyl group. c and d each represent a single bond, the bond position of the bond c is the 10th or 11th position, and the bond position of the bond d is the 14th or 15th position. n1 and n2 each independently represent 0 or 1, and n3 represents 1 and 2. )
In addition, the pigment | dyes represented by the said general formula (IX)-(XII) may be in the state of a salt, respectively, and may form the complex with arbitrary metals.
[7]
[5] An ink composition for ink jet using the ink composition according to [6].
[8]
An ink set comprising at least one ink composition according to any one of [3] to [7].
[9]
An ink jet recording method using the ink composition according to any one of [3] to [7].
[10]
[9] The method according to [9], wherein an image is formed by using the ink composition according to [3] to [7] on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support. Inkjet recording method.
[11]
A colored body, wherein an image is formed by the method according to [9] and [10].
[12]
An ink jet printer cartridge comprising the ink composition according to any one of [3] to [7].
[13]
[12] An ink jet printer comprising the ink jet printer cartridge according to [12].
The present invention relates to the above [1] to [13], but other matters are also described for reference.
(1) A dye represented by the following general formula (I), wherein the dye satisfies one or both of the following conditions:
Condition 1: R ₁ and R ₁ ′ are a hydrogen atom or a substituent having no ionic hydrophilic group and hydroxy group.
Condition 2: The absolute value of the difference between λmax (DMF) and λmax (water) is 50 nm or less.
λmax (DMF) and λmax (water) are defined as follows. That is, a solution prepared by DMF: water = 98: 2 at 25 ° C. and 0.002% is put in a cell having a thickness of 10 mm, and the maximum absorption wavelength in the visible region of the absorption spectrum measured with a spectrophotometer is λmax ( DMF), and similarly, the maximum absorption wavelength of the absorption spectrum measured in an aqueous solvent is λmax (water).

In general formula (I), Ar ₁ and Ar ₁ ′ each represent a monovalent aromatic carbocyclic ring, and Ar ₂ , Ar ₂ ′, Ar ₃ and Ar ₃ ′ each represent a divalent aromatic carbocyclic linkage. Represents a group. Here, at least one of Ar ₁ , Ar ₂ and Ar ₃ represents a naphthalene ring, and at least one of Ar ₁ ′, Ar ₂ ′ and Ar ₃ ′ represents a naphthalene ring. A represents a substituent represented by the following general formulas (II) to (IV) or a divalent or higher valent linking group represented by the general formula (V), and R ₁ , R ₁ ′, R ₂ and R ₃ are Represents a hydrogen atom or a substituent, Q represents a divalent or higher linking group, and q represents an integer of 2 or higher.

(2) The dye according to (1), wherein the absolute value of the difference between λmax (DMF) and λmax (water) is 30 nm or less in Condition 2.
(3) The dye according to (1) or (2), wherein the general formula (I) is represented by the following general formula (VII).

In formula (VII), R ₄ , R ₄ ′, R ₅ , R ₅ ′, R ₆ and R ₆ ′ each independently represents a hydrogen atom or a substituent. L ₁ , L ₁ ′, L ₂ and L ₂ ′ each independently represent an ionic hydrophilic group, and m, m ′, n and n ′ each represent an integer of 1 to 2. A represents a substituent represented by the following general formulas (II) to (IV), or a divalent or higher linking group represented by the general formula (V),

In general formulas (II) to (IV), R ₁ , R ₁ ′, R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. In general formula (V), Q is divalent. The above linking groups are represented, and q represents an integer of 2 or more.
(4) The dye according to (3), wherein the following general formula (VII) is represented by the following general formula (VIII).

  In general formula (VIII), M represents a hydrogen atom, a metal cation, or an organic cation. A represents a substituent represented by the following general formulas (II) to (IV), or a divalent or higher linking group represented by the general formula (V),

In general formulas (II) to (IV), R ₁ , R ₁ ′, R ₂ and R ₃ each independently represent a hydrogen atom or a substituent, and in general formula (V), Q is divalent or higher. Q represents an integer of 2 or more.
(5) A dye represented by the following general formula (VII):

In formula (VII), R ₄ , R ₄ ′, R ₅ , R ₅ ′, R ₆ and R ₆ ′ each independently represents a hydrogen atom or a substituent. L ₁ , L ₁ ′, L ₂ and L ₂ ′ each independently represent an ionic hydrophilic group, and m, m ′, n and n ′ represent an integer of 1 to 2. A represents a substituent represented by the following general formulas (II) to (IV) and (VI), or a divalent or higher linking group represented by the general formula (V),

In general formulas (II) to (IV), R ₁ , R ₁ ′, R ₂ and R ₃ each independently represent a hydrogen atom or a substituent, and in general formula (V), Q is divalent or higher. Q represents an integer of 2 or more. In general formula (VI), X represents a halogen atom.
However, R ₁ and R ₁ ′ are not simultaneously a 2-hydroxyethyl group, and when R ₁ is a hydrogen atom, R ₁ ′ is a 2-hydroxyethyl group, a 2-sulfoethyl group, and a sulfonylaryl group. There is nothing. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
(6) The dye according to (5), wherein the general formula (VII) is represented by the following general formula (VIII).

  In formula (VIII), M represents a hydrogen atom, a metal cation, or an organic cation. A represents a substituent represented by the following general formulas (II) to (IV) and (VI), or a divalent or higher linking group represented by the general formula (V),

In general formulas (II) to (IV), R ₁ , R ₁ ′, R ₂ and R ₃ each independently represent a hydrogen atom or a substituent, and in general formula (V), Q is divalent or higher. Q represents an integer of 2 or more. In general formula (VI), X represents a halogen atom.
However, R ₁ and R ₁ ′ are not simultaneously a 2-hydroxyethyl group, and when R ₁ is a hydrogen atom, R ₁ ′ is a 2-hydroxyethyl group, a 2-sulfoethyl group, and a sulfonylaryl group. There is nothing.
(7) An ink composition comprising at least one dye according to any one of (1) to (6).
(8) The ink composition as described in (7), which is for inkjet.
(9) An ink composition comprising at least one dye according to any one of (1) to (6) and having a dye having an absorption maximum on a longer wavelength side than the dye.
(10) The dye having absorption on the long wavelength side is at least one dye selected from dyes represented by the following general formulas (IX), (X), (XI) and (XII) ( The ink composition according to 9).

(In the general formula (IX), Ar ₄ represents a substituted or unsubstituted monovalent aromatic group or a substituted or unsubstituted monovalent heterocyclic group. R ₇ represents a substituted or unsubstituted aromatic group. (Excluding an unsubstituted phenyl group) or a substituted or unsubstituted heterocyclic group (excluding an unsubstituted thiophene ring group) Y represents —CR ₉ ═ or a nitrogen atom, and Y represents —CR ₉ ═ And R ₉ represents a hydrogen atom or a substituent, and B ₁ and B ₂ each represent = CR ₁₀ -and -CR ₁₁ =, or either one is a nitrogen atom and the other is = CR ₁₀ -Or -CR ₁₁ = represents G. R ₈ , R ₈ ', R ₁₀ and R ₁₁ each independently represents a hydrogen atom or a substituent.

(In the general formula (X), Ar ₅ , Ar ₆ and Ar ₇ represent a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group. Z represents either a hydroxy group or an amino group. .)

(In the general formula (XI), Ar ₈ and Ar ₉ represent a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group. A and b each represents a single bond, and a bond of a bond a The position is the 2nd or 3rd position, and the bonding position of the bond b is the 6th or 7th position, m1 and m3 each independently represent 0 or 1, and m2 represents 1 and 2.)

(In the general formula (XII), Ar ₁₀ represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group. R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or a substituent. C and d each represent a single bond, the bond position of the bond c is the 10th or 11th position, and the bond position of the bond d is the 14th or 15th position. Represents 0 or 1, and n3 represents 1 and 2.)
In addition, the pigment | dyes represented by the said general formula (IX)-(XII) may be in the state of a salt, respectively, and may form the complex with arbitrary metals.
(11) An ink composition for ink jet using the ink composition according to (9) and (10).
(12) An ink set comprising at least one ink composition as described in (7) to (11).
(13) An ink jet recording method using the ink composition according to (8) or (11).
(14) An image is formed using the ink composition according to (8) or (11) above on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support ( The inkjet recording method as described in 13).
(15) A colored product obtained by forming an image by the method described in (13) and (14).
(16) An ink jet printer cartridge comprising the ink composition according to (8) or (11).
(17) An ink jet printer comprising the ink jet printer cartridge according to (16).

  The black ink composition of the present invention has sufficient solution stability, and has a good black tone and a high print density by an ink jet recording ink and an ink jet recording method using the black ink composition. Moreover, it is possible to form an image having high fastness against light and the active gas in the environment, and image bleeding and color change during storage under high humidity and high temperature are greatly improved.

  Hereinafter, the present invention will be described in more detail.

[dye]
The water-soluble dye containing the single compound of the present invention has an absorption maximum at 440 to 540 nm and a half-value width at 90 nm to 200 nm in a visible absorption spectrum in a solvent prepared with DMF: water = 98: 2. , A dye that achieves broad absorption.
In the present specification, the term “single compound” means a compound that is not a plurality of compounds having different physical properties. That is, when a visible region absorption spectrum is measured, combining a plurality of compounds does not indicate physical properties such as a desired absorption maximum and a half-value width, but indicates that such a physical property is exhibited by one compound.

Since the dye has such an absorption characteristic, it can absorb a wide range of light from blue to green, which tends to be insufficient in the absorption spectrum of the disazo dye or the trisazo dye, and is preferable as a color correction dye. Have
The absorption maximum of the dye is preferably between 450 and 520 nm,
It is particularly preferable that the thickness is 500 nm.
The full width at half maximum of the dye is preferably between 100 nm and 180 nm, and particularly preferably between 110 nm and 160 nm.

Commercially available dyes having the above absorption characteristics include C.I. I. Direct Red 84, Brown 106, and Brown 202 are useful, and can be used for color tone adjustment of many black pigments, and is excellent in color development, fastness, and fixing properties. I. Direct Red 84 is particularly useful. However, C.I. I. Direct Red 84 is a compound with a very strong cohesive force, and when preparing an ink, it is necessary to add an organic solvent to ensure ink storage stability, and the urea bond is susceptible to hydrolysis, It is hard to say that it has sufficient performance due to safety concerns.
Further, although a dye linked via a triazine is also described in Patent Document 6, although resistance to hydrolysis action is improved, a problem remains regarding ink storage stability. Furthermore, these dyes have the problem that after printing on inkjet paper, they undergo a significant color change (short wavelength) under high humidity and high temperature, and it is difficult to say that they have sufficient performance.
As a result of intensive studies on the remarkable color change (short wavelength) under high humidity and high temperature, the present inventors have found that this problem can be solved by using a dye having the following conditions. Ie

A dye represented by the following general formula (I), wherein the dye satisfies one or both of the following conditions:
Condition 1: R ₁ , R ₁ ′, R ₂ and R ₃ are a hydrogen atom or a substituent having no ionic hydrophilic group and hydroxy group.
Condition 2: The absolute value of the difference between λmax (DMF) and λmax (water) is 50 nm or less.
[In the visible region of the absorption spectrum measured with a solvent prepared with DMF: water = 98: 2, the maximum absorption wavelength is λmax (DMF), and the maximum absorption wavelength of the absorption spectrum measured with a water solvent is λmax (water). . ].

In general formula (I), Ar ₁ and Ar ₁ ′ each represent a monovalent aromatic carbocyclic ring, and Ar ₂ , Ar ₂ ′, Ar ₃ and Ar ₃ ′ each represent a divalent aromatic carbocyclic linkage. Represents a group. Here, at least one of Ar ₁ , Ar ₂ and Ar ₃ represents a naphthalene ring, and at least one of Ar ₁ ′, Ar ₂ ′ and Ar ₃ ′ represents a naphthalene ring. A represents a substituent represented by the following general formulas (II) to (IV) or a divalent or higher valent linking group represented by the general formula (V), and R ₁ , R ₁ ′, R ₂ and R ₃ Represents a hydrogen atom or a substituent, Q represents a divalent or higher linking group, and q represents an integer of 2 or higher. Q is preferably divalent or trivalent, and divalent is particularly preferable. q is preferably 2 or 3, and 2 is particularly preferred. )

The aromatic hydrocarbon rings constituting the Ar ₁ , Ar ₁ ′, Ar ₂ , Ar ₂ ′, Ar _3, and Ar ₃ ′ groups include a benzene ring and a naphthalene ring, and these rings further include a hydrocarbon ring, a hetero ring It may be condensed with a ring or the like.

The ionic hydrophilic group represented by L ₁ , L ₁ ′, L ₂ and L ₂ ′ in formula (VII) will be described. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are generally used, and a carboxyl group or a sulfo group is particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) and the like. As the number of ionic hydrophilic groups, those having at least two in one molecule of the dye of the present invention are preferable, and those having at least two (more preferably four or more) sulfo groups and / or carboxyl groups are particularly preferable.

The color change under high humidity and high temperature is considered to be caused by a decrease in reflection density due to association of pigments in paper and bleeding in the depth direction.
As a result of intensive studies to solve this problem, the present inventors have found that the degree of color change varies greatly depending on the nature of the substituent A. For example, in a compound in which the substituent A is substituted with a 2-sulfoethyl group or a 2-hydroxyethyl group, it is recognized that the reflection density decreases. On the other hand, it was found that a decrease in reflection density can be suppressed in a compound having no 2-sulfoethyl group or 2-hydroxylethyl group as the substituent A.
_'Each Examples of the substituent of preferably a hydrogen atom or an alkyl group, R ₁ and _{R 1'} R _1, R ₁ bonded to each other with the ring (preferably 5- to 8-membered ring) . When _{one of} R ₁ and R ₁ ′ is a hydrogen atom and the other is an alkyl group, both are alkyl groups, or R ₁ and R ₁ ′ are bonded to each other to form a 5-membered or 6-membered ring (preferably Is more preferably a 6-membered ring, and both are more preferably alkyl groups. The alkyl group and the 5-membered ring or 6-membered ring further include a hydroxyl group, an alkoxy group, a carboxyl group, a sulfo group, an aryl group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group. A group, an amide group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfonamide group, a sulfamoyl group, a cyano group and a nitro group.
As an example of substitution of R ₂ and R ₃ , an alkyl group or an aryl group is preferable. The alkyl group and aryl group are further halogen, sulfo group, alkoxy group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, amide group, carbamoyl group, sulfonyl group, sulfinyl group. , A sulfonamido group, a sulfamoyl group, a cyano group and a nitro group.

  Examples of the most preferable substituent A include a dialkylamino group, and a dialkylamino group having 1 to 12 carbon atoms in total is particularly preferable. This suggests that increasing the water-solubility of the dye causes the dye to ooze out under high humidity and high temperature, causing a decrease in reflection density. In particular, when the coloring matter is used for adjusting the color tone of the black coloring matter, it is clear that this reduction in reflection density leads to a marked reduction in the color tone balance, thereby reducing the quality of the printed image.

  Further, it was recognized that when the association property of the dye became strong, the color changed greatly (short wavelength) under high humidity and high temperature. This is considered to be due to the association of the dyes under high humidity and high temperature. The strength of the associative property of the dye is considered to be approximately approximated by the absolute value of the difference between λmax (DMF) and λmax (water), and the absolute value of the difference between λmax (DMF) and λmax (water) is 50 nm or less. A pigment | dye is preferable and a pigment | dye of 30 nm or less is more preferable.

  Examples of preferred compounds are shown below, but the preferred embodiments of the present invention are not limited to the following examples. In the following general formula, the dye is represented by a free acid structure, but it goes without saying that it may be used in the form of a salt in actual use. Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

Further, the substituent A in the general formula (I) may be a divalent or higher valent linking group represented by the general formula (V). In particular, when the dye molecules are twisted due to the linking group, the effect of suppressing the association between the molecules works, and thus it was confirmed that the color change (short wavelength) under high humidity and high temperature is suppressed. Although the example of a preferable pigment | dye is shown with the structure of a free acid below, it cannot be overemphasized that you may use as arbitrary salts. * In a formula shows the coupling | bond part with a triazine ring.
Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

  As the dye having absorption on the long wavelength side, dyes represented by the following general formulas (IX), (X), (XI) and (XII) are preferable.

In General Formula (IX), Ar ₄ represents a substituted or unsubstituted monovalent aromatic group or a substituted or unsubstituted monovalent heterocyclic group. R ₇ represents a substituted or unsubstituted aromatic group (excluding an unsubstituted phenyl group) or a substituted or unsubstituted heterocyclic group (excluding an unsubstituted thiophene ring group). Y represents —CR ₉ ═ or a nitrogen atom, and when Y is —CR ₉ ═, R ₉ represents a hydrogen atom or a substituent. B ₁ and B ₂ each represent = CR ₁₀ -and -CR ₁₁ =, or either one represents a nitrogen atom and the other represents = CR ₁₀ -or -CR ₁₁ =. G, R ₈ , R ₈ ′, R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a substituent.

In the general formula _{(X), Ar 5, Ar} 6 and Ar ₇ represents a substituted or unsubstituted aromatic group or substituted or unsubstituted heterocyclic group. Z represents either a hydroxy group or an amino group.

In General Formula (XI), Ar ₈ and Ar ₉ represent a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group. a and b each represent a single bond, the bond position of the bond a is the 2nd or 3rd position, and the bond position of the bond b is the 6th or 7th position. m1 and m3 each independently represent 0 or 1, and m2 represents 1 and 2.

In General Formula (XII), Ar ₁₀ represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group. R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or a substituent. c and d each represent a single bond, the bond position of the bond c is the 10th or 11th position, and the bond position of the bond d is the 14th or 15th position. n1 and n2 each independently represent 0 or 1, and n3 represents 1 and 2.
In addition, the pigment | dyes represented by the said general formula (IX)-(XII) may be in the state of a salt, respectively, and may form the complex with arbitrary metals.
Examples of preferred dyes having absorption on the long wavelength side are shown in the form of a free acid, but it goes without saying that they may be used as arbitrary salts.
Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

  In addition to the dyes represented by the above formula, JP-A-10-130557, JP-A-9-255906, JP-A-7-975541, JP-A-6-234944, European Patent Application Publication No. 982371, JP-A-2002 -302619, 2002-327131, 2002-265809, International Publication Nos. 00/043450, 00/043451, 00/043452, 00/043453, 03/106572, The dyes described in each pamphlet of No. 03/104332 can also be preferably used as a dye having absorption on the long wavelength side.

  The black ink composition of the present invention preferably contains 0.2 to 30% by mass, particularly preferably 0.5 to 15% by mass, and most preferably 1 to 10% by mass of the dye having absorption on the long wavelength side in the ink. % Content is preferable.

  The ratio of the dye having absorption on the short wavelength side and the dye having absorption on the long wavelength side of the present invention is 1 to 50 masses of the dye having absorption on the short wavelength side with respect to the dye having absorption on the long wavelength side. %, More preferably 5 to 40% by mass, and most preferably 10 to 30% by mass.

[ink]
The ink of the present invention means an ink containing at least one water-soluble coloring matter of the present invention. The ink of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording.

  The ink of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium and dissolving and / or dispersing the dye of the present invention in the medium. Preferably, an aqueous medium is used. As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water miscible organic solvent include those described in JP-A No. 2003-306623. In addition, the said water miscible organic solvent may use 2 or more types together. The ink of the present invention includes an ink composition excluding a medium.

  The ink of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives (refer Unexamined-Japanese-Patent No. 2003-306623), such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, and a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink.

  The method for preparing the ink for ink jet recording is described in detail in JP-A-5-295212, JP-A-7-97541, and JP-A-7-82515 in addition to the above-mentioned patent documents. It can also be used for preparing ink jet recording inks.

  In the inkjet ink of the present invention, other pigments may be used in combination with the pigment of the present invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably 0.1 parts by mass or more and 30 parts by mass or less in 100 parts by mass of the ink jet recording ink, and 0.2 parts by mass The content is more preferably 20 parts by mass or less, and still more preferably 0.5 to 15 parts by mass.

  The ink of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full-color image, in addition to the ink of the present invention, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and two-color inks can be used for each color. Furthermore, an intermediate tone ink such as blue or orange can be used.

  As the dye that can be used in the ink for ink-jet recording and the ink of each color used for forming a full-color image in the present invention, any pigment can be used. For example, paragraph number of JP-A-2003-306623 Each dye described in 0090 to 0092 can be used.

[Inkjet recording method]
In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. To do.
As the image receiving material, an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support is preferable. The description of paragraph numbers 0093 to 0105 of JP-A No. 2003-306623 can be applied as the ink jet recording method of the present invention.

  In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition location may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, JP 2002-166638, JP 2002-121440, JP 2002-154201, JP 2002-144696, JP 2002-080759, Japanese Patent Application 2000-299465, and Japanese Patent Application 2000. The method described in -297365 can be preferably used.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-1316648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element. Pulse method), acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink, and thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
Although the synthesis example of this invention is shown below, it can synthesize | combine by the same method also about dyes other than this. In the text, “part” is based on mass.

  1 to 100 parts of a bisazo compound represented by the following formula is dissolved in 200 parts of water, and 15.4 parts of cyanuric chloride is suspended in 90 parts of water and cooled with ice at a temperature of 3 to 5 ° C. Drip while maintaining. After the dropwise addition, an aqueous solution obtained by dissolving 9.5 parts of sodium carbonate in 50 parts of water is added dropwise while maintaining a temperature of 3 to 5 ° C. After stirring for 30 minutes while maintaining the temperature, the reaction temperature is raised to 35 ° C. and stirring is continued for 3 hours. 540 ml of isopropanol is added dropwise to the reaction solution, and the precipitated product is filtered, washed with isopropanol and dried. After drying, 97.6 parts of compound 2 were obtained. Λmax of Compound 2 in an aqueous solvent was 414.9 nm.

Compound 2 and 50.0 parts were dissolved in a mixed solvent of 250 parts of water and 250 parts of dimethylacetamide, to which 5.3 parts of di-n-butylamine and 10.3 parts of sodium hydrogen carbonate were added and kept at 70 ° C. Stir for 5 hours. 500 ml of isopropanol is added dropwise to the reaction solution, and the precipitated product is filtered, washed with isopropanol and dried. The obtained product was dissolved again in water and made into a lithium salt using an ion exchange resin (AMBERLITE ^(R) manufactured by Organo Corp.) substituted with a lithium cation. After distilling off the water and drying, 47.6 parts of dye 5-Li were obtained. The λmax (DMF) and λmax (water) of the dye 5-Li were 483.2 nm and 471.3 nm, respectively.

  In the same manner as in Example 2, except that 5.3 parts of di-n-butylamine of Example 2 was changed to 3.7 parts of a 50 wt% dimethylamine aqueous solution, 45.0 parts of the following dye 2-Li was obtained. The λmax (DMF) and λmax (water) of the dye 2-Li were 482.0 nm and 419.1 nm, respectively.

  In the same manner as in Example 2, except that 5.3 parts of dibutylamine in Example 2 was changed to 4.6 parts of methylcyclohexylamine, 42.6 parts of the following dye 8-Li was obtained. The λmax (DMF) and λmax (water) of the dye 8-Li were 483.0 nm and 434.3 nm, respectively.

  46.3 parts of the following dye 12-Li was obtained in the same manner as in Example 2 except that 5.3 parts of dibutylamine in Example 2 was changed to 4.8 parts of n-butylethylamine. The λmax (DMF) and λmax (water) of the dye 12-Li were 482.9 nm and 447.6 nm, respectively.

  The following dye 58-Li 38.6 parts were obtained in the same manner as in Example 2 except that 5.3 parts of dibutylamine of Example 2 was changed to 2.3 parts of trans-1,2-cyclohexyldiamine. The λmax (DMF) and λmax (water) of the dye 58-Li were 481.5 nm and 458.4 nm, respectively.

[Comparative Example 1]
As a comparative example for the present invention, the following comparative dye A-Li, which is a lithium salt of the short wave dye 10 described in Patent Document 6, was synthesized. The comparative dye A-Li had λmax (DMF) and λmax (water) of 483.0 nm and 425.5 nm, respectively.

[Comparative Example 2]
As another comparative example, the following comparative dye B-Li, which is a lithium salt of the compound example described in JP-A No. 2005-146244 (described in Table 14), was synthesized. The comparative dye B-Li had λmax (DMF) and λmax (water) of 483.2 nm and 421.3 nm, respectively.

[Comparative Example 3]
Furthermore, as another comparative example, the following comparative dye C-Li, which is a lithium salt of short wave dye 2 described in Patent Document 6, was synthesized. The comparative dye C-Li had λmax (DMF) and λmax (water) of 477.4 nm and 470.1 nm, respectively.

(A-1) Preparation of monochromatic ink The following components were mixed and then stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, each ink composition was prepared by filtration under reduced pressure using a microfilter having an average pore diameter of 0.25 μm.

In the above table, the unit amount is mass.

(A-2) Preparation of mixed-color ink A black ink was prepared by separately synthesizing a lithium salt of dye 60 (dye 60-Li) as a dye on the long wavelength side and combining it with the dye of the present invention. Each ink composition was prepared by the same method as described above using the following components.

  In the above table, the unit amount is mass.

(B) Inkjet printing These inks were loaded into an ink cartridge of an inkjet printer PM-920 manufactured by EPSON, and an inkjet image was formed using an inkjet paper “Image” photofinishing manufactured by Fuji Photo Film Co., Ltd.

1) For the evaluation of hue, for single color inks, A is the one where the absorption maximum in the reflection spectrum is in the range of 480 nm to less than 510 nm, B is the one in the range of 440 nm to less than 480 nm and 510 nm to 540 nm, and the others are C. did. For mixed color (black) ink, a gray staircase pattern is used to visually determine the gray color tone at each print density, and A indicates a preferred gray color tone at each density, and a density where the gray balance is broken is scattered. Is B, and C is the gray balance that is lost at most densities.

2) Regarding the storage stability of the ink, each of the prepared inks was allowed to stand at 70 ° C. for 6 days, and estimated by high-performance liquid chromatography (HPLC) and change in absorption intensity of the solution absorption spectrum. A sample showing a residual rate of 95% or more at 70 ° C. for 6 days was designated as A, a sample having 90% to 95% was designated as B, and a sample having less than C was designated as C.
3) Regarding the image storability under high humidity and high temperature, the change in the reflection spectrum under the conditions of 70% humidity and 80 ° C. for 7 days was measured for the inkjet image using the monochromatic ink. The change in the absorption maximum of the reflection spectrum before and after the conditions is expressed as Δλmax value, and the ratio of the reflection density is expressed as ROD value (= OD value (after time) / OD value (before time)). Evaluation was performed.

Regarding mixed color (black) ink, the gray color tone at each printing density is visually judged by a gray staircase pattern, and the one showing a preferable gray color tone at each density is A, and the density at which the gray balance is broken is scattered. B was designated as C, and C as the gray balance was lost at most densities.
The results are shown below.

  From the above results, it can be seen that the ink liquid using the coloring matter of the present invention exhibits excellent hue and ink stability as well as excellent image storage stability at high temperature and high humidity.

Claims (13)

Dyes, characterized by being represented by the following general formula (VII).

In the general formula _{(VII), R 4, R} 4 ', R 5, R 5', R 6 and _{R 6} 'represents a water MotoHara child. L ₁ , L ₁ ′, L ₂ and L ₂ ′ each independently represent an ionic hydrophilic group, and m, m ′, n and n ′ represent an integer of 1 to 2. A represents a substituent or Formula communication Yuimoto that you express by (V), represented by the following formula (II),

In general formula (II ), R ₁ and R ₁ ′ each independently represent a hydrogen atom , an alkyl group, or a cyclohexyl group , and in general formula (V), Q represents the following general formulas (XX) to (XXV) ) Represents a divalent to trivalent linking group, and q represents 2 or 3 . In general formula (VI), X represents a halogen atom.

However, R ₁ and R ₁ ′ may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the alkyl group, cyclohexyl group, 5-membered ring and 6-membered ring are further a hydroxyl group, an alkoxy group , Carboxyl group, sulfo group, aryl group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, amide group, carbamoyl group, sulfonyl group, sulfinyl group, sulfonamide group, sulfamoyl group , May have a cyano group and a nitro group. Further, R ₁ and R _{1 'are} not equal to 2-hydroxyethyl group at the same time, and R ₁ is R ₁ when hydrogen _atoms' becomes the 2-hydroxyethyl group, 2-sulfoethyl group and sulfonyl aryl group There is nothing. The dye according to claim 1 , wherein the general formula (VII) is represented by the following general formula (VIII).

In general formula (VIII), M represents a hydrogen atom, a metal cation, or an organic cation. A represents a substituent or Formula communication Yuimoto that you express by (V), represented by the following formula (II),

In general formula (II ), R ₁ and R ₁ ′ each independently represent a hydrogen atom , an alkyl group, or a cyclohexyl group , and in general formula (V), Q represents the following general formulas (XX) to (XXV) ) Represents a divalent to trivalent linking group, and q represents 2 or 3 . In general formula (VI), X represents a halogen atom.

However, R ₁ and R ₁ ′ may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the alkyl group, cyclohexyl group, 5-membered ring and 6-membered ring are further a hydroxyl group, an alkoxy group , Carboxyl group, sulfo group, aryl group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, amide group, carbamoyl group, sulfonyl group, sulfinyl group, sulfonamide group, sulfamoyl group , May have a cyano group and a nitro group. Further, R ₁ and R _{1 'are} not equal to 2-hydroxyethyl group at the same time, and R ₁ is R ₁ when hydrogen _atoms' becomes the 2-hydroxyethyl group, 2-sulfoethyl group and sulfonyl aryl group There is nothing. An ink composition comprising at least one dye according to claim 1 or 2 . 4. The ink composition according to claim 3 , wherein the ink composition is for inkjet. An ink composition comprising a dye containing at least one dye according to claim 1 or 2 and having an absorption maximum on a longer wavelength side than the dye. Dyes having an absorption maximum to the long wavelength side, the following general formula (IX), (X), according to claim 5, characterized in that at least one dye of the dye represented by (XI) and (XII) The ink composition described in 1.

In General Formula (IX), Ar ₄ represents a monovalent aromatic group that may be substituted with a sulfo group . R ₇ represents Fang Kozokumoto (excluding only Shi full Eniru group). Y represents -C H = or a nitrogen atom. B ₁ and B ₂ each represent = CR ₁₀ -and -CR ₁₁ =, or either one represents a nitrogen atom and the other represents = CR ₁₀ -or -CR ₁₁ =. R ₁₀ and R ₁₁ each independently represents a hydrogen atom, a methyl group or a cyano group. G represents an aryl amino group which may be substituted by a sulfo group, R _8, and R _{8 'each} independently represent a hydrogen atom or a sulfo aryl group which may be substituted by group.

In general formula (X), Ar ₅ represents an aromatic group that may be substituted with a nitro group and a sulfo group, and Ar ₆ is an aromatic group that may be substituted with a sulfo group or a sulfo group and a hydroxyl group. the stands, Ar ₇ is to display the aromatic group which may be substituted, or a sulfo group, heterocyclic group which may be substituted by an oxo group and an aryl group, nitro group and the sulfo group, the aryl group further sulfo It may be substituted by a group. Z represents either a hydroxy group or an amino group.

In General Formula (XI), Ar ₈ represents an aromatic group that may be substituted with an alkoxy group and a sulfo group, and Ar ₉ represents an aromatic group that may be substituted with a sulfo group . a and b each represent a single bond, the bond position of the bond a is the 2nd or 3rd position, and the bond position of the bond b is the 6th or 7th position. m1 and m3 each independently represent 0 or 1, and m2 represents 1 and 2. )

In General Formula (XII), Ar ₁₀ is an aromatic group that may be substituted with a sulfo group. Represents. R ₁₂ represents a hydrogen atom or an aryl group, R ₁₃ represents an alkoxy group which may be substituted with a hydrogen atom or a sulfo group, and R ₁₄ each independently represents a hydrogen atom or an alkyl group. c and d each represent a single bond, the bond position of the bond c is the 10th or 11th position, and the bond position of the bond d is the 14th or 15th position. n1 and n2 each independently represent 0 or 1, and n3 represents 1 and 2. )
In addition, the pigment | dyes represented by the said general formula (IX)-(XII) may be in the state of a salt, respectively, and may form the complex with arbitrary metals. An ink composition for ink jet, wherein the ink composition according to claim 5 or 6 is used. An ink set comprising at least one ink composition according to claim 3 . An ink jet recording method using the ink composition according to claim 3 . Claim on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support, characterized in that the image formed using the ink composition according to any of the claims 3-7 9 The ink jet recording method described in 1. Color bodies, characterized in that the image formed by the method of claim 9 and 10. An ink jet printer cartridge comprising the ink composition according to claim 3 . An ink jet printer loaded with the ink jet printer cartridge according to claim 12 .