JP2006328129A - Ink composition, inkjet recording method, method for preventing bronzing, and colored matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition suited for inkjet recording, having a good hue as a cyan ink, being excellent in light resistance, ozone resistance, and moisture resistance, and scarcely undergoing bronzing. <P>SOLUTION: The ink composition comprises a copper phthalocyanine dye having sulfonylurea groups as substituents or a salt thereof represented by formula (I) (wherein CuPc is a copper phthalocyanine skeleton) and a copper phthalocyanine dye having alkylsulfonyl groups as substituents or a salt thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink composition, a method for suppressing a bronze phenomenon using the ink composition, an ink jet recording method, and a colored body.

  A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is what you do. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material do not contact each other and is quiet with little sound generation, and is easy to downsize and speed up. Expected. Conventionally, water-based inks in which water-soluble dyes are dissolved in an aqueous medium have been used as inks such as fountain pens, felt-tip pens, and ink-jet recording inks. In order to prevent clogging of ink, a water-soluble organic solvent is generally added. For this reason, these conventional inks provide a recording image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, and have little bleeding. It is required that a bronze phenomenon (also referred to as a bronzing phenomenon) does not easily occur on the material, and that storage stability is excellent. Further, the formed image is required to have image fastness such as water resistance, light resistance, ozone gas resistance and moisture resistance.

The bronze phenomenon refers to a phenomenon in which the dye becomes a piece of metal on the surface of the recording material due to the association of the dye or poor absorption of the ink, and so on. When this phenomenon occurs, the glossiness, print quality, and print density are all inferior. In particular, when a metal phthalocyanine dye is used as a coloring material, it often appears as a red floating phenomenon in a portion printed at a high density, and the color balance of the entire image becomes uneven and the image quality is deteriorated. The improvement is desired.
In recent years, glossy paper has been widely used as a recording medium with a texture close to that of a photographic tone, but due to the bronze phenomenon of specific colors, the glossiness on the surface of the printed matter varies, and the image Therefore, the improvement is strongly desired from the viewpoint of maintaining the glossiness of the entire image.

  Ozone gas resistance is usually called ozone resistance or gas resistance, but this means that ozone gas with an oxidizing action present in the air reacts with dyes in recording paper and discolors the printed image. It is resistance to the phenomenon. In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx, SOx, etc., but the reason why ozone gas promotes the color fading phenomenon of ink jet recording images more than these oxidizing gases. It is considered a substance. Ozone gas is used in the acceleration test to know the degree of ozone gas resistance. Such a discoloration and fading phenomenon caused by an oxidizing gas is characteristic of an ink jet image, so that improvement of ozone gas resistance has become a more important issue. In particular, the ink receiving layer provided on the surface of photographic image quality inkjet paper uses a porous material such as a white inorganic pigment to speed up ink drying and reduce bleeding at high image quality. In many cases, discoloration due to ozone gas is noticeable on such recording paper.

  Typical skeletons of water-soluble cyan dyes used in ink jet recording inks are phthalocyanine and triphenylmethane. In recent years, from the viewpoint of improving image fastness, the most extensive report on the improvement of pigments has been reported, and phthalocyanine dyes are used as inks. In particular, phthalocyanine dyes with improved ozone resistance were used. Bronze phenomenon is conspicuous in cyan ink, and its improvement is demanded.

  In the future, in order to expand the field of use of printing methods using ink, it is expected that the types of recording materials for ink-jet recording will increase. Therefore, ink that can be used in various applications and environments is required. ing. Among them, as a cyan ink, there is a high technical demand for suppressing the bronze phenomenon as much as possible while maintaining a high level of ozone resistance.

Regarding the creation of such a cyan ink, for example, as disclosed in Patent Documents 1 to 4, a technique of suppressing a bronze phenomenon by using a dye having good ozone resistance and adding an additive has been reported. However, the use of that method alone is not effective enough to be called.
Further, as cyan dyes having good ozone resistance, for example, those of Patent Documents 5 to 11 have been proposed. When inks using these are used, a bronzing phenomenon is observed depending on the type of recording material and the printing density. In some cases, it is not possible to supply cyan ink that sufficiently satisfies market demands from the viewpoint of suppressing bronzing.

JP 2003-31478 A JP 2004-91630 A JP 2004-91631 A JP 2004-263155 A Japanese Patent Laid-Open No. 2002-249677 JP 2002-275386 A JP 2002-294097 A JP 2002-302623 A JP 2002-327132 A JP 2003-003099 A JP 2003-213168 A

  An object of the present invention is to solve the above-mentioned conventional problems, have an excellent hue as a cyan ink, and have excellent image fastness such as light resistance, ozone resistance and moisture resistance while suppressing a bronze phenomenon. And, further, to provide an ink jet recording method.

（式中、R₂、R₃及びR₄はそれぞれ独立に水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアリ−ル基、置換もしくは無置換のヘテロ環基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアルケニル基を、Ａは架橋基を、Ｂはヘテロ原子を表す。Ｂが２価のヘテロ原子の場合R₄は存在しない。隣接するR₃、R₄、Ａ及びＢどうしが互いに連結して環を形成しても良い。Ｚは窒素原子または置換された炭素原子を表す。Ｘ及びＹはそれぞれ独立してハロゲン原子、水酸基、スルホ基、カルボキシル基、アミノ基、置換もしくは無置換の含窒素ヘテロ環基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のシクロアルコキシ基、置換もしくは無置換のアリロキシ基、置換もしくは無置換のヘテロ環オキシ基、置換もしくは無置換のアラルキルオキシ基、置換もしくは無置換のアルケニルオキシ基、置換もしくは無置換のアルキルアミノ基、置換もしくは無置換のシクロアルキルアミノ基、置換もしくは無置換のアリ−ルアミノ基、置換もしくは無置換のヘテロ環アミノ基、置換もしくは無置換のアラルキルアミノ基、置換もしくは無置換のアルケニルアミノ基、置換もしくは無置換のジアルキルアミノ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のシクロアルキルチオ基、置換もしくは無置換のアリ−ルチオ基、置換もしくは無置換のヘテロ環チオ基、置換もしくは無置換のアラルキルチオ基、置換もしくは無置換のアルケニルチオ基を表す。また、Ｘ及びＹのうち少なくとも１つはイオン性親水性基を置換基として有する基である。）で表される置換基を有し、下記式（ｑ）

−SO₂R₅ （ｑ）

（式中、R₅は、１つ以上のイオン性親水性基を置換基として有していても良いアルキル基を表す。）で表される置換基を有しない銅フタロシアニン染料又はその塩と、上記式（ｑ）で表される置換基を有し、上記式（Ｑ）で表される置換基を有しない銅フタロシアニン染料又はその塩を含有する、上記（１）に記載のインク組成物、
（５）
スルホニルウレア基を置換基として有する銅フタロシアニン染料又はその塩を（Ｉ）、アルキルスルホニル基を置換基として有する銅フタロシアニン染料又はその塩を（ＩＩ）とした場合、（Ｉ）が下記式（１）

（式中ＣｕＰｃは銅フタロシアニン骨格を表し、R₁、R₂、R₃及びR₄はそれぞれ独立に水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアリ−ル基、置換もしくは無置換のヘテロ環基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアルケニル基を、Ａは架橋基を、Ｂはヘテロ原子を表す。Ｂが２価のヘテロ原子の場合R₄は存在しない。隣接するR₃、R₄、Ａ及びＢどうしが互いに連結して環を形成しても良い。Ｚは窒素原子または置換された炭素原子を表す。Ｘ及びＹはそれぞれ独立してハロゲン原子、水酸基、スルホ基、カルボキシル基、アミノ基、置換もしくは無置換の含窒素ヘテロ環基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のシクロアルコキシ基、置換もしくは無置換のアリロキシ基、置換もしくは無置換のヘテロ環オキシ基、置換もしくは無置換のアラルキルオキシ基、置換もしくは無置換のアルケニルオキシ基、置換もしくは無置換のアルキルアミノ基、置換もしくは無置換のシクロアルキルアミノ基、置換もしくは無置換のアリ−ルアミノ基、置換もしくは無置換のヘテロ環アミノ基、置換もしくは無置換のアラルキルアミノ基、置換もしくは無置換のアルケニルアミノ基、置換もしくは無置換のジアルキルアミノ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のシクロアルキルチオ基、置換もしくは無置換のアリ−ルチオ基、置換もしくは無置換のヘテロ環チオ基、置換もしくは無置換のアラルキルチオ基、置換もしくは無置換のアルケニルチオ基を表す。また、Ｘ及びＹのうち少なくとも１つはイオン性親水性基を置換基として有する基である。また、ａ＝０〜２、ｂ＝０〜４、ｃ＝０〜３であり、かつａ＋ｂ＋ｃ＝２〜４である。）
で表され、また（ＩＩ）が、下記式（２）

（式中、R₅〜R₈はそれぞれ独立に置換若しくは無置換のアルキル基を表す。但し、R₅〜R₈の少なくとも１つ以上はイオン性親水性基を置換基として有する。）
で表されることを特徴とする上記（１）から（４）のいずれか一項に記載のインク組成物、
（６）
（Ｉ）の銅フタロシアニン染料又はその塩を酸化分解した際に、モル比率で、得られたスルホフタル酸誘導体中の６０％以上が４−スルホフタル酸誘導体である上記（１）から（５）のいずれか一項に記載のインク組成物、
（７）
（Ｉ）が下記式（３）

（式中、R₁、R₂、R₃、R₄、Ｘ、Ｙ、Ｚは前記式（１）と同じ意味を表す。ａ、ｂ、ｃも同様に前記式（１）と同じ意味を表す。）
で表される上記（１）から（６）のいずれか一項に記載のインク組成物、
（８）
R₁、R₂、R₃及びR₄が水素原子、Ｃ１からＣ８のアルキル基（スルホ基、カルボキシル基、水酸基、アルコキシ基、ジアルキルアミノ基、アセチルアミノ基、シアノ基、アリールチオ基からなる群から選択される置換基で置換されても良い）、Ｃ３からＣ７のシクロアルキル基（カルボキシル基、水酸基、ジアルキルアミノ基、アセチルアミノ基からなる群から選択される置換基で置換されても良い）またはアラルキル基（スルホ基で置換されても良い）である上記（１）から（７）のいずれか一項に記載のインク組成物、
（９）
Ａがアルキレン、シクロアルキレン、アリレンであり、Ｂが硫黄原子及び窒素原子であり、R₄が水素原子（Ｂが硫黄原子のときはR₄は存在しない）である上記（１）から（８）のいずれか一項に記載のインク組成物、
（１０）
Ｚにおける置換された炭素原子の置換基がハロゲン原子、カルボキシル基またはホルミル基である上記（１）から（９）のいずれか一項に記載のインク組成物、
（１１）
Ｘ及びＹがそれぞれ独立して、塩素原子、水酸基、アミノ基、カルボキシル基、スルホ基、アルコキシ基（スルホ基、カルボキシル基、水酸基、ジアルキルアミノ基、アリールアミノ基、アセチルアミノ基、アルコキシ基、アリール基、シアノ基、ハロゲン原子、アリールチオ基で置換されても良い）、フェノキシ基（スルホ基、カルボキシル基、ウレイド基、アルキル基、アルコキシ基、ジアルキルアミノ基、アセチルアミノ基から選択される１種または２種以上の置換基で置換されても良い）、ナフトキシ基（スルホ基、カルボキシル基、アセチルアミノ基、アリールアミノ基から選択される１種または２種以上の置換基で置換されても良い）、ベンジロキシ基（ベンゼン核がスルホ基で置換されても良い）、フェネチルオキシ基（ベンゼン核がスルホ基で置換されても良い）、アルキルアミノ基（スルホ基、カルボキシル基、水酸基、ジアルキルアミノ基、アリールアミノ基、アセチルアミノ基、アルコキシ基、アリール基、シアノ基、ハロゲン原子、アリールチオ基で置換されても良い）、アニリノ基（スルホ基、カルボキシル基、ウレイド基、アルキル基、アルコキシ基、水酸基、ジアルキルアミノ基、アセチルアミノ基、シアノ基、ニトロ基、ハロゲン原子、ヘテロ環基から選択される１種または２種以上の置換基で置換されても良い）、ナフチルアミノ基（スルホ基、カルボキシル基、ウレイド基、アルキル基、アルコキシ基、水酸基、ジアルキルアミノ基、アセチルアミノ基、シアノ基、ニトロ基、ハロゲン原子、ヘテロ環基から選択される１種または２種以上の置換基で置換されても良い）、ベンジルアミノ基（ベンゼン核がスルホ基で置換されても良い）、フェネチルアミノ基（ベンゼン核がスルホ基で置換されても良い）、アルキルチオ基（スルホ基、カルボキシル基、水酸基で置換されても良い）、アリールチオ基(スルホ基、カルボキシル基、水酸基、アルキル基から選択される１種または２種以上の置換基で置換されても良い)およびモルホリン−４−イル基である上記（１）から（１０）のいずれか一項に記載のインク組成物、
（１２）
R₁〜R₄が水素、イソプロピル基及びヒドロキシエチル基であり、Ａがエチレン、ブチレン及びへキシレンであり、Ｂが窒素原子または硫黄原子（ただしＢが硫黄原子の場合、R₄は存在しない）であり、Ｘが水酸基、スルホ基、カルボキシル基及びニトロ基を有していても良いアニリノ基又はアニリノ基と同じ置換基を有していても良いナフチルアミノ基であり、Ｙがスルホエチル基、メトキシ基、水酸基、カルボキシメチル基、ヒドロキシエチル基を置換基として有しても良いアミノ基又はモルホリノ基であり、Ｚが窒素原子である、上記（１）に記載の染料またはその塩、
（１３）
R₅〜R₈がそれぞれ独立に、炭素数２〜５のアルキル基（アルコキシ基、水酸基、カルボキシル基、スルホ基、置換基を有しても良いアルコキシ基、置換基を有しても良いアルコキシアルコキシ基、置換基を有しても良いアミド基、置換基を有しても良いスルホンアミド基から選択される１種または２種以上の置換基で置換されても良い）である上記（１）から（１２）のいずれか一項に記載のインク組成物、
（１４）
R₅〜R₈がそれぞれ独立に、炭素数２〜５のアルキル基（スルホ基、水酸基、置換基を有しても良いスルホンアミド基から選択される１種または２種の置換基で置換されても良い）である上記（１）から（１３）のいずれか一項に記載のインク組成物、
（１５）
（Ｉ）の銅フタロシアニン染料又はその塩の可視光領域における水中での最大吸収波長が、６０８〜６２０ｎｍである上記（１）から（１４）のいずれか一項に記載のインク組成物、
（１６）
インク組成物中の総ての色素中で、（Ｉ）の銅フタロシアニン染料又はその塩がモル比率で１０〜８０％を占める上記（１）から（１５）のいずれか一項に記載のインク組成物、
（１７）
インクジェット記録用である上記（１）から（１６）のいずれか一項に記載のインク組成物、
（１８）
上記（１７）に記載のインク組成物を用いたインクジェット記録方法、
（１９）
上記（１）から（１８）のいずれか一項に記載のインク組成物を用いたブロンズ現象の抑制方法、
（２０）
被記録材が情報伝達用シートである上記（１８）に記載のインクジェット記録方法、
（２１）
被記録材が、白色無機微粒子を用いた微細な多孔質構造をインク吸収層として持つ、吸収型メディアと呼ばれる情報伝達用シートである上記（２０）に記載のインクジェット記録方法、
（２２）
上記（１７）から（２１）のいずれか一項に記載の方法で着色された着色体、
に関する。 The present inventors have studied in detail phthalocyanine dyes having good hue, light resistance and ozone resistance, and by mixing two kinds of specific phthalocyanine dyes to prepare an ink composition, The present inventors have found that the problem can be solved and have completed the present invention. That is, the present invention
(1)
An ink composition comprising a copper phthalocyanine dye or a salt thereof having a sulfonylurea group as a substituent, and a copper phthalocyanine dye or a salt thereof having an alkylsulfonyl group as a substituent;
(2)
The mixing ratio of the copper phthalocyanine dye or salt thereof having a sulfonylurea group as a substituent and the copper phthalocyanine dye or salt thereof having an alkylsulfonyl group as a substituent is from 10:90 to 80:20 by mass ratio (above ( 1) The ink composition according to
(3)
The ink composition according to the above (1), wherein the proportion of the dye mixture contained in the ink composition is 0.5 to 8% by mass when the concentration is high, and 0.1 to 2.5% by mass when the concentration is low. object,
(4)
Following formula (Q)

Wherein R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, A represents a bridging group, B represents a heteroatom, and when B is a divalent heteroatom, R ₄ does not exist. Adjacent R ₃ , R ₄ , A and B may be connected to each other to form a ring, Z represents a nitrogen atom or a substituted carbon atom, and X and Y independently represent a halogen atom or a hydroxyl group. , Sulfo group, carboxyl group, amino group, substituted or unsubstituted nitrogen-containing heterocyclic group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkoxy group, substituted or unsubstituted allyloxy Substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or Unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted An alkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio group; And at least one of X and Y Have a substituent represented by the ionic hydrophilic group is a group having as a substituent.), The following equation (q)

-SO ₂ R ₅ (q)

(Wherein R ₅ represents an alkyl group optionally having one or more ionic hydrophilic groups as a substituent), a copper phthalocyanine dye having no substituent or a salt thereof, The ink composition according to (1), comprising a copper phthalocyanine dye or a salt thereof having a substituent represented by the formula (q) and not having a substituent represented by the formula (Q);
(5)
When the copper phthalocyanine dye or salt thereof having a sulfonylurea group as a substituent is (I) and the copper phthalocyanine dye or salt thereof having an alkylsulfonyl group as a substituent is (II), (I) is represented by the following formula (1)

(Wherein CuPc represents a copper phthalocyanine skeleton, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group, An aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, A represents a bridging group, B represents a heteroatom, and B represents a divalent atom. In the case of a hetero atom, R ₄ does not exist, adjacent R ₃ , R ₄ , A and B may be connected to each other to form a ring, Z represents a nitrogen atom or a substituted carbon atom. Y is independently a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a substituted or unsubstituted nitrogen-containing heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloal Coxi group, substituted or unsubstituted allyloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or Unsubstituted cycloalkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted Dialkylamino group, substituted or unsubstituted alkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted aralkylthio group A substituted or unsubstituted alkenylthio group In addition, at least one of X and Y is a group having an ionic hydrophilic group as a substituent, a = 0 to 2, b = 0 to 4, c = 0 to 3, and a + b + c = 2-4.)
And (II) is represented by the following formula (2):

(In the formula, R _{5 to} R ₈ each independently represents a substituted or unsubstituted alkyl group, provided that at least one of R _{5 to} R ₈ has an ionic hydrophilic group as a substituent.)
The ink composition according to any one of (1) to (4), wherein the ink composition is represented by:
(6)
When the copper phthalocyanine dye of (I) or a salt thereof is oxidatively decomposed, 60% or more of the obtained sulfophthalic acid derivative is a 4-sulfophthalic acid derivative in molar ratio, any of (1) to (5) above Or an ink composition according to claim 1,
(7)
(I) is the following formula (3)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , X, Y, Z represent the same meaning as in the formula (1). A, b, and c also have the same meaning as in the formula (1). To express.)
The ink composition according to any one of (1) to (6), which is represented by:
(8)
R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, C1 to C8 alkyl groups (from the group consisting of sulfo group, carboxyl group, hydroxyl group, alkoxy group, dialkylamino group, acetylamino group, cyano group and arylthio group) A C3 to C7 cycloalkyl group (which may be substituted with a substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a dialkylamino group and an acetylamino group) or The ink composition according to any one of (1) to (7) above, which is an aralkyl group (which may be substituted with a sulfo group);
(9)
(1) to (8) above, wherein A is alkylene, cycloalkylene, and arylene, B is a sulfur atom and a nitrogen atom, and R ₄ is a hydrogen atom (R ₄ does not exist when B is a sulfur atom). The ink composition according to any one of
(10)
The ink composition according to any one of (1) to (9), wherein the substituent of the substituted carbon atom in Z is a halogen atom, a carboxyl group, or a formyl group,
(11)
X and Y are each independently a chlorine atom, hydroxyl group, amino group, carboxyl group, sulfo group, alkoxy group (sulfo group, carboxyl group, hydroxyl group, dialkylamino group, arylamino group, acetylamino group, alkoxy group, aryl 1 group selected from a group, a cyano group, a halogen atom and an arylthio group), a phenoxy group (sulfo group, carboxyl group, ureido group, alkyl group, alkoxy group, dialkylamino group, acetylamino group) A naphthoxy group (which may be substituted with one or more substituents selected from a sulfo group, a carboxyl group, an acetylamino group and an arylamino group) , Benzyloxy group (benzene nucleus may be substituted with sulfo group), phenethyloxy group (ben Nuclei may be substituted with sulfo groups), alkylamino groups (sulfo groups, carboxyl groups, hydroxyl groups, dialkylamino groups, arylamino groups, acetylamino groups, alkoxy groups, aryl groups, cyano groups, halogen atoms, arylthio groups. Anilino group (sulfo group, carboxyl group, ureido group, alkyl group, alkoxy group, hydroxyl group, dialkylamino group, acetylamino group, cyano group, nitro group, halogen atom, heterocyclic group) A naphthylamino group (sulfo group, carboxyl group, ureido group, alkyl group, alkoxy group, hydroxyl group, dialkylamino group, acetylamino group, cyano) One or more selected from a group, a nitro group, a halogen atom, and a heterocyclic group A benzylamino group (the benzene nucleus may be substituted with a sulfo group), a phenethylamino group (the benzene nucleus may be substituted with a sulfo group), an alkylthio group (a sulfo group, A carboxyl group and a hydroxyl group), an arylthio group (which may be substituted with one or more substituents selected from a sulfo group, a carboxyl group, a hydroxyl group and an alkyl group) and morpholine-4- The ink composition according to any one of (1) to (10), which is an yl group,
(12)
R _{1 to} R ₄ are hydrogen, isopropyl group and hydroxyethyl group, A is ethylene, butylene and hexylene, B is a nitrogen atom or a sulfur atom (provided that B is a sulfur atom, R ₄ is not present) X is an anilino group which may have a hydroxyl group, a sulfo group, a carboxyl group and a nitro group, or a naphthylamino group which may have the same substituent as the anilino group, and Y is a sulfoethyl group, a methoxy group A dye or a salt thereof according to (1) above, which is an amino group or morpholino group optionally having a group, a hydroxyl group, a carboxymethyl group, a hydroxyethyl group as a substituent, and Z is a nitrogen atom,
(13)
R _{5 to} R ₈ are each independently an alkyl group having 2 to 5 carbon atoms (alkoxy group, hydroxyl group, carboxyl group, sulfo group, alkoxy group which may have a substituent, alkoxy which may have a substituent) It may be substituted with one or two or more substituents selected from an alkoxy group, an amide group that may have a substituent, and a sulfonamide group that may have a substituent. ) To (12), the ink composition according to any one of
(14)
R _{5 to} R ₈ are each independently substituted with one or two substituents selected from an alkyl group having 2 to 5 carbon atoms (a sulfo group, a hydroxyl group, and a sulfonamide group which may have a substituent). The ink composition according to any one of (1) to (13) above,
(15)
The ink composition according to any one of (1) to (14) above, wherein the maximum absorption wavelength in water in the visible light region of the copper phthalocyanine dye of (I) or a salt thereof is 608 to 620 nm,
(16)
The ink composition according to any one of (1) to (15), wherein the copper phthalocyanine dye of (I) or a salt thereof accounts for 10 to 80% in a molar ratio among all the pigments in the ink composition. object,
(17)
The ink composition according to any one of (1) to (16), which is for inkjet recording,
(18)
An inkjet recording method using the ink composition according to (17),
(19)
A method of suppressing a bronze phenomenon using the ink composition according to any one of (1) to (18),
(20)
The inkjet recording method according to (18), wherein the recording material is an information transmission sheet,
(21)
The inkjet recording method according to (20), wherein the recording material is an information transmission sheet called an absorption medium having a fine porous structure using white inorganic fine particles as an ink absorption layer,
(22)
A colored body colored by the method according to any one of (17) to (21),
About.

  The ink composition of the present invention has an excellent hue as a cyan ink and is excellent in image fastness such as light resistance, ozone resistance and moisture resistance while suppressing a bronze phenomenon. In addition, there is no crystal precipitation, physical property change, color change, etc. after long-term storage, and storage stability is good. Furthermore, when used together with other magenta ink and yellow ink, a color tone in a wide visible region can be produced. Therefore, the cyan composition of the present invention is extremely useful as an ink for inkjet recording.

  The present invention will be described in detail. The ink suitable for inkjet recording of the present invention is an ink composition in which at least two kinds of copper phthalocyanine dyes or salts (I) and (II) thereof are mixed, and one of them (I) is particularly represented by the above formula. (1) and (II) are particularly represented by the formula (2). The present invention comprises a copper phthalocyanine dye having a sulfonylurea group as a substituent or a salt thereof represented by the formula (1), and a copper phthalocyanine dye having an alkylsulfonyl group represented by the formula (2) or a salt thereof. It has been found that the mixed ink composition is excellent in ozone resistance and suppression of the bronze phenomenon.

  In general, copper phthalocyanine derivatives inevitably contain substitution position isomers of substituents in the synthesis thereof, but these substitution position isomers are often regarded as the same derivatives without being distinguished from each other. In this specification, for convenience, three types of phthalocyanine derivatives having different substitution positions are defined below.

(1) β-position substitution type: A 4-sulfophthalic acid derivative can be obtained upon oxidative decomposition.
(2) α-position substitution type: A 3-sulfophthalic acid derivative is obtained upon oxidative decomposition.
(3) α, β-position mixed substitution type: A mixture of 3-sulfophthalic acid and 4-sulfophthalic acid is obtained upon oxidative decomposition.

The above β-position substitution type, α-position substitution type, and α, β-position mixed substitution type phthalocyanine dyes, which are decomposed into phthalic acid derivatives with nitric acid or the like, are replaced by NMR or high performance liquid chromatography. It can be discriminated by examining the position. If the β-substituted phthalocyanine derivative is decomposed, the 4-substituted phthalic acid derivative is obtained. If the α-substituted phthalocyanine derivative is decomposed, the 3-substituted phthalic acid derivative is obtained. If the derivative decomposes the α, β-position mixed substitution type phthalocyanine derivative, a 3-position substituted and a 4-position substituted phthalic acid derivative can be obtained, respectively.
Examples of the oxidizing agent used for the oxidative decomposition of the phthalocyanine dye include nitric acid and ozone. The conditions for the oxidative decomposition include, for example, when nitric acid is used as the oxidizing agent, 60% by weight of 20 to 50 times the phthalocyanine dye. By treating in concentrated nitric acid at 100 ° C. for 5 to 30 minutes, it can be decomposed into a phthalic acid derivative.

  The copper phthalocyanine dye or salt (I) used in the ink composition of the present invention may be any of β-position substitution type, α-position substitution type, α, β-position mixed substitution type, and β-position substitution type. It is preferable that the position substitution type or α, β-position mixed substitution type is used, and in this case, in particular, in the case of the α, β-position mixed substitution type, those having a higher proportion of 4-sulfophthalic acid upon oxidative decomposition are preferred The molar ratio is preferably 60% or more. The most preferred is a β-position substitution type, which is represented by the formula (3).

Unless otherwise specified in the present specification, the number of carbon atoms in the alkyl group, alkoxy group, alkylamino group, alkylthio group, alkenyl group, alkenyloxy group, alkenylamino group, cycloalkyl group, cycloalkoxy group, cycloalkylamino group, etc. Is not particularly limited as long as the object of the present invention is achieved. Usually, those carbon numbers are 1-16, Preferably it is 1-12, More preferably, it is 1-6, Furthermore, it is 1-4. However, about a cycloalkyl group, it is 3-12 normally, Preferably it is 5-8. Moreover, when these have a substituent, as long as the objective of this invention is achieved, the kind of the substituent is not specifically limited. Preferred substituents on the carbon chain of these groups include, for example, a sulfo group and a group derived therefrom (such as a sulfamoyl group), a carboxyl group and a group derived therefrom (such as a carboxylic acid ester group), a phosphono group, and a derivative thereof. Groups (such as phosphate ester groups), hydroxyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted amino groups, substituted or unsubstituted aryl groups, halogen atoms, cyano groups, substituted or unsubstituted arylthio groups Etc.
The aryl group is not particularly limited as long as the object of the present invention is achieved. Usually, it is a phenyl group or a naphthyl group. These may be condensed with a heterocycle or the like. Preferred substituents on the aryl group include, for example, those mentioned as preferred substituents on the above carbon chain, ureido groups, nitro groups, heterocyclic groups and the like.

In the above formulas (1) and (3), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, substituted or An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, A represents a bridging group, and B represents a heteroatom. When B is a divalent hetero atom, R ₄ does not exist. Adjacent R ₃ , R ₄ , A and B may be connected to each other to form a ring.

  Examples of the substituted or unsubstituted alkyl group include an alkyl group having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), an aryl group, a halogen atom, a cyano group, an arylthio group ( And may be substituted with a sulfo group or the like.

  Examples of the substituted or unsubstituted cycloalkyl group include cycloalkyl groups having 3 to 12 carbon atoms. Preferably, a C5-C8 cycloalkyl group is mentioned. Examples of the substituent on the cycloalkyl ring include a sulfo group, a carboxyl group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), an aryl group, a halogen atom, and cyano. Group, an arylthio group (which may be substituted with a sulfo group or the like).

  The number of carbon atoms of the alkyl group in the alkyl group (aralkyl group) substituted with the aryl group is preferably about 1 to 12. The aralkyl group may have a substituent. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), and a ureido Group, alkyl group, alkoxy group, nitro group, cyano group, heterocyclic group and halogen atom.

  Examples of the substituted or unsubstituted aryl group include a phenyl group and a naphthyl group. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), a ureido group, an alkyl group, an alkoxy group, a nitro group, and a cyano group. , A heterocyclic group, and a halogen atom. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable. These may be condensed with a heterocycle and may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of the aryl group condensed with a heterocycle include benzothiazole, benzisothiazole, benzimidazole, benzotriazole, benzoxazole, and the like.

  The substituted or unsubstituted heterocyclic group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, Examples include oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocycles may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, or an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, and halogen atom.

  Examples of the substituted or unsubstituted alkenyl group include alkenyl groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done.

Preferred R ₁ , R ₂ , R ₃ and R ₄ may be substituted with a hydroxy group such as a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group or a hydroxyethyl group (C 1- C4) substituted or unsubstituted alkyl group; (C1-C4) alkyl group substituted with a sulfo group such as sulfoethyl group, sulfopropyl group, etc .; (C1-C4) alkyl substituted with a carboxyl group such as carboxyethyl group A sulfo group, a sulfo-substituted arylthio (C1-C4) alkyl group; a phenyl group or a naphthyl group substituted with a sulfo group, a carboxyl group or a hydroxyl group; a di [sulfo (C1-C4) alkyl] amino (C1-C4) alkyl group; It is done.

Examples of the bridging group A include alkylene, cycloalkylene, and arylene, and may be a group formed by combining these. Examples of the group formed by combining these include xylylene. Moreover, the group which contained the hetero atom in the bridge | crosslinking group may be sufficient. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the group formed by combining these include 3-oxa-1,5-pentanediyl and 4-aza-1,7-heptanediyl. It is done. Or it may form a crosslinked group together with R ₃ and R _4. The cross-linking group may have a substituent. Examples of the substituent include a sulfo group, a carboxyl group, and a hydroxyl group.

  Examples of the alkylene include alkylene having 1 to 16 carbon atoms. Some of the alkylene carbon atoms may be substituted with nitrogen, oxygen and sulfur atoms. Further, it may be a group formed by combining alkylene and cycloalkylene.

  Examples of cycloalkylene include cycloalkylene having 1 to 16 carbon atoms. Some of the carbon atoms of the cycloalkylene may be substituted with nitrogen, oxygen and sulfur atoms. Further, it may be a group formed by combining cycloalkylene and alkylene. Cycloalkylene may be a bridged cyclic hydrocarbon or a spirocyclic hydrocarbon.

  Examples of the arylene include phenylene and naphthylene. These may have a substituent. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), a ureido group, an alkyl group, an alkoxy group, a nitro group, and a cyano group. Group and halogen atom.

  Examples of the hetero atom B include nitrogen, oxygen, sulfur, silicon, phosphorus, and selenium. Preferred heteroatoms are nitrogen, oxygen and sulfur atoms. Nitrogen and sulfur atoms are particularly preferable.

  In the formula (1) or (3), Z represents a nitrogen atom or a substituted carbon atom. Examples of the substituent of the substituted carbon atom include a halogen atom, a formyl group, and a carboxyl group.

  In the formula (1) or (3), X and Y are each independently a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a substituted or unsubstituted nitrogen-containing heterocyclic group, a substituted or unsubstituted alkoxy group. Group, substituted or unsubstituted cycloalkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted Substituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenyl Amino group, substituted or unsubstituted dialkylamino group, substituted Is an unsubstituted alkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio Represents a group. Further, at least one of X and Y has an ionic hydrophilic group as a substituent. As the ionic hydrophilic group, an anionic hydrophilic group is preferable, and examples thereof include a sulfo group, a carboxyl group, and a phosphono group. These ionic hydrophilic groups may be free forms, or may be alkali metal salts, alkaline earth metal salts, onium ion salts or ammonium salts of organic amines. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include calcium and magnesium. As the organic amine, examples of the alkylamine include lower alkylamines having 1 to 4 carbon atoms such as methylamine and ethylamine. Examples of the alkanolamine include mono-, di- or tri (lower alkanol having 1 to 4 carbon atoms) amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. Preferred are salts with ammonium, sodium, potassium, lithium, monoethanolamine, diethanolamine, trienolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like.

  The substituted or unsubstituted nitrogen-containing heterocyclic group is preferably a 5-membered or 6-membered ring, which may be further condensed. Further, it may be a nitrogen-containing aromatic heterocycle or a nitrogen-containing non-aromatic heterocycle, but a nitrogen-containing non-aromatic heterocycle is more preferred. Examples of nitrogen-containing heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, Examples include benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperazine, imidazolidine, thiazoline, morpholine, piperidine and the like. These heterocycles may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, or an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, and halogen atom.

  As said substituted or unsubstituted alkoxy group, a C1-C12 alkoxy group is mentioned, for example. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  As said substituted or unsubstituted cycloalkoxy group, a C1-C12 cycloalkoxy group is mentioned, for example. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted allyloxy group include a phenoxy group and a naphthoxy group. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), a ureido group, an alkyl group, an alkoxy group, a nitro group, and a cyano group. A group, a heterocyclic group, and a halogen atom. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  The substituted or unsubstituted heterocyclic oxy group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, Examples include oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocycles may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (an alkyl group, an aryl group, a sulfoalkyl group, or an acetyl group). A ureido group, an alkyl group, an alkoxy group, a nitro group, a cyano group, and a halogen atom.

  As said substituted or unsubstituted aralkyloxy group, a C1-C12 aralkyloxy group is mentioned, for example. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkenyloxy group include alkenyloxy groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkylamino group include alkylamino groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, a sulfo-substituted alkyl group, an aryl group or an acetyl group), an aryl group, and a halogen atom. And a cyano group. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted cycloalkylamino group include cycloalkylamino groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted arylamino group include an anilino group and a naphthylamino group. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), a ureido group, an alkyl group, an alkoxy group, a nitro group, and a cyano group. A group, a heterocyclic group, and a halogen atom. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  The substituted or unsubstituted heterocyclic amino group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, Examples include oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocycles may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, or an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, halogen atom and oxy group.

  As said substituted or unsubstituted aralkylamino group, a C1-C12 aralkylamino group is mentioned, for example. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkenylamino group include alkenylamino groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkylthio group include an alkylthio group having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted cycloalkylthio group include cycloalkylthio groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a naphthylthio group. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (which may be substituted with an alkyl group, an aryl group or an acetyl group), a ureido group, an alkyl group, an alkoxy group, a nitro group, and a cyano group. A group, a heterocyclic group, and a halogen atom. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  The substituted or unsubstituted heterocyclic thio group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, Examples include oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocycles may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, or an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, and halogen atom.

  As said substituted or unsubstituted aralkylthio group, a C1-C12 aralkylthio group is mentioned, for example. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkenylthio group include alkenylthio groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, or an acetyl group), an aryl group, a halogen atom, and a cyano group. It is done. Of these, a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group are preferable.

Particularly preferred groups as R _{1 to} R ₄ in the formula (1) are a hydrogen atom, iso-propyl, 2-hydroxyethyl and the like, and particularly preferred groups as the bridging group A are ethylene, n-butylene and n-hexylene. And particularly preferable as B is a nitrogen atom and a sulfur atom (when B is a sulfur atom, R ₄ is not present), and particularly preferable as Z is selected from a nitrogen atom, a chlorine atom, a formyl group, and a carboxyl group The carbon atom which may be substituted with a group, and a particularly preferable group as X is an anilino group which may have a sulfo group, a hydroxyl group, a carboxyl group or a nitro group as a substituent, or the same substituent as the anilino group. A naphthylamino group which may have, and particularly preferred groups as Y are a hydroxyl group, a methoxy group, a morpholino group, a sulfoethyl group, a sulfopro group. An amino group or a sulfopropylthio group which may have a pill group, a carboxymethyl group or a hydroxyethyl group as a substituent.
A particularly preferred combination of R _{1 to} R ₄ , A, B, X, Y and Z in formula (1) is that R ₁ , R ₂ and R ₃ are hydrogen, A is ethylene, and B is a sulfur atom. (When B is a sulfur atom, R ₄ is not present), X is an anilino group which may have a sulfo group or a nitro group as a substituent, and Y has a morpholino group or a sulfoethyl group as a substituent. And R _{1 to} R ₄ are hydrogen, A is ethylene, butylene, hexylene, B and Z are nitrogen atoms, and X is a hydroxyl group. , A sulfo group, an anilino group which may have a carboxyl group or a naphthylamino group which may have the same substituent as the anilino group, and Y is a methoxy group, a hydroxyl group, a sulfoethyl group, a carboxymethyl group, Has hydroxyethyl group as a substituent May be an amino group or a sulfopropylthio group; and R ₁ is an isopropyl group or a hydroxyethyl group, R ₂ is an isopropyl group or a hydroxyethyl group, and R _{3 to} R ₄ are hydrogen, A is ethylene, B and Z are nitrogen atoms, X is an anilino group which may have a sulfo group, and Y is an amino group.

In the formula (1) or (3) of the present invention, the number a of the sulfo group is 0 to 2, the number b of the substituted or unsubstituted sulfamoyl group is 0 to 4, and the number c of the substituted sulfonylurea group is 0 to 3 and the total number a + b + c of these substituents is 2 to 4.
As an average value in the copper phthalocyanine dye or salt thereof represented by the formula (1) or (3) of the present invention, the a is 0 to 2, preferably 1.5 or less, more preferably 1. 0 or less, b is 0 or more and less than 4, preferably 1.0 to 3.5, more preferably 1.5 to 3.0, and c is greater than 0 and 3 or less, preferably Is 0.5 to 3.0, more preferably 1.0 to 2.0.
When the value of a is large, the ozone resistance tends to be low, but it is difficult to eliminate the sulfo group completely in production. On the other hand, if the value of b is large, the ozone resistance becomes high, while the bronze phenomenon tends to occur. Therefore, in consideration of ozone resistance, bronze characteristics, ease of production, etc., the number of sulfo groups, sulfamoyl groups and sulfonylurea groups may be adjusted as appropriate to select a balanced ratio.

The copper phthalocyanine dye (II) used in the ink composition of the present invention is represented by the general formula (2). In the general formula (2), R ₅ to R ₈ each independently represents a substituted or unsubstituted alkyl group. However, at least one of R ₅ to R ₈ has an ionic hydrophilic group as a substituent. The carbon chain of the substituted or unsubstituted alkyl group may be linear or branched, and the number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 6.
Examples of the substituent for substituting the alkyl group include a hydroxyl group, a carboxyl group, a sulfone group, and an alkoxy group (which may be further substituted with an alkyl group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group, or a sulfo group), and a carbamoyl group. (May be substituted by an alkyl group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a sulfo group), a sulfamoyl group (by an alkyl group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a sulfo group) And may be substituted). As the ionic hydrophilic group, a sulfo group or a carboxyl group is preferable, and a sulfo group is particularly preferable.
As a preferable group in R _{5 to} R ₈ in the formula (3), a group selected from a sulfo group, a hydroxyl group, a methoxy group, and a sulfonamide group which may have a substituent may be included as a substituent. n-propyl group or n-butyl group.
Particularly preferred R _{5 to} R ₈ are 3-sulfo-n-propyl group, 4-sulfo-n-butyl group, 2-hydroxy-3-sulfo-n-propyl group, 3-sulfo-n-butyl group, 3-[(1-carboxy-2-hydroxy) ethylamino] sulfonyl-n-propyl, 3-[(2-methyl-n-butyl) amino] sulfonyl-n-propyl, 3-[(2,3-dihydroxy -N-propyl) amino] sulfonyl-n-propyl, 3-[(2-hydroxy-n-propyl) amino] sulfonyl-n-propyl, 3-[(2-ethyl-n-hexyl) amino] sulfonyl-n -Propyl, 3-[(2-methoxy-n-propyl) amino] sulfonyl-n-propyl, 3-[(1-methyl-n-propyl) amino] sulfonyl-n-propyl.

  Both the copper phthalocyanine dye or the salts (I) and (II) thereof used in the ink composition of the present invention may be present as a free acid or may form a salt. At this time, (I) and (II) may not be the same form. Examples of these salts include alkali metal salts, onium salts of organic amines, ammonium salts, and the like. Sodium salts, lithium salts, and ammonium salts are preferable, and lithium salts are particularly preferable.

Specific examples of combinations of sulfamoyl groups; sulfonylurea groups of compounds in which a = b = c = 1 in the copper phthalocyanine dye or salt thereof represented by the formula (1) or (3) of the present invention are shown in Tables 1 to 8 Shown in However, actual a, b, and c are average values. Further, the copper phthalocyanine dye or salt (I) used in the ink composition of the present invention is not limited to the following examples. In the table, the sulfonylurea group is described in the form of a free acid.

Specific examples of the substituents R ₅ to R _{8 in} the copper phthalocyanine dye (II) used in the ink composition of the present invention are shown in Tables 9 to 11. In the table, the carboxyl group and the sulfo group which are ionic water-soluble groups are described in the form of free acid.
Table 12 shows specific combinations of substituents in the copper phthalocyanine dye (II).

[Table 12]
R ₅ R ₆ R ₇ R ₈
2-1 2-1 2-1 2-1
2-1 2-1 2-1 2-5
2-1 2-1 2-5 2-5
2-1 2-1 2-1 2-6
2-1 2-1 2-1 2-7
2-1 2-1 2-1 2-8
2-1 2-1 2-1 2-9
2-1 2-1 2-1 2-10
2-1 2-1 2-1 2-11
2-1 2-1 2-1 2-12
2-1 2-1 2-1 2-13
2-1 2-1 2-1 2-15
2-1 2-1 2-15 2-15
2-1 2-15 2-15 2-15
2-1 2-1 2-1 2-16
2-1 2-1 2-16 2-16
2-1 2-16 2-16 2-16
2-1 2-1 2-1 2-17
2-1 2-1 2-17 2-17
2-1 2-17 2-17 2-17
2-1 2-1 2-1 2-18
2-1 2-1 2-18 2-18
2-1 2-18 2-18 2-18
2-1 2-1 2-1 2-21
2-1 2-1 2-21 2-21
2-1 2-1 2-1 2-22
2-1 2-1 2-22 2-22
2-1 2-1 2-1 2-23
2-1 2-1 2-1 2-24
2-2 2-2 2-2 2-2
2-2 2-2 2-2 2-14
2-2 2-2 2-14 2-14
2-2 2-2 2-2 2-19
2-2 2-2 2-2 2-20
2-3 2-3 2-3 2-3
2-4 2-4 2-4 2-4
2-6 2-6 2-6 2-6
2-7 2-7 2-7 2-7
2-11 2-11 2-11 2-11
2-12 2-12 2-12 2-12
2-13 2-13 2-13 2-13
2-14 2-14 2-14 2-14
2-18 2-18 2-18 2-18
2-20 2-20 2-20 2-20

The copper phthalocyanine dye or its salt (I) used in the ink composition of the present invention is converted to a sulfamoyl group by reacting copper phthalocyanine sulfonic acid chloride with ammonia or a primary organic amine, and further condensing a carbamate compound to the sulfamoyl group. It can be obtained by converting to a group.
In order to obtain copper phthalocyanine sulfonic acid chloride, it can be obtained by reacting copper phthalocyanine with chlorosulfonic acid, or 4-sulfophthalic acid derivatives or 4-sulfophthalic acid derivatives and phthalic acid derivatives in the presence of a copper compound. It can also be obtained by reacting a compound obtained by the reaction with a chlorinating agent to convert a sulfo group to a chlorosulfone group, and then reacting with ammonia or a primary organic amine to convert to a sulfamoyl group.
In the former case, an α, β-position mixed substitution type phthalocyanine dye is obtained (analysis of a phthalic acid derivative decomposed with nitric acid by NMR reveals that the ratio of the 3-position substituted phthalic acid derivative to the 4-position substituted phthalic acid derivative is approximately 50. : 50), in the latter case, a β-position substituted phthalocyanine dye is obtained. In particular, in order to obtain an ink having high ozone resistance, a β-position substituted phthalocyanine dye obtained by the latter method is preferable. When the β-position substitution type is synthesized, 4-sulfophthalic acid used as a raw material usually contains about 15 to 25% by mass of 3-sulfophthalic acid as an impurity, and the α-position substitution product derived therefrom is contained in the target phthalocyanine dye. Mixed. In order to further enhance the effect of the present invention (particularly in order to obtain an ink having high ozone resistance), it is preferable to use a raw material having a low content of 3-sulfophthalic acid. Further, in the obtained copper phthalocyanine dye or a salt thereof, a product in which a chlorosulfone group is partially decomposed during the reaction is mixed in the reaction product, but there is no particular problem.

  The copper phthalocyanine dye or its salt (I) used in the ink composition of the present invention is represented by the following formula (1), and it is preferable that a β-substituted product is a main component.

[In the formula (1), R ₁ , R ₂ , R ₃ , R ₄ , X, Y and Z have the same meaning as described above. a, b and c also have the same meaning as described above. ]

A method for producing the copper phthalocyanine dye of formula (1) or a salt thereof used in the ink composition of the present invention will be described. Here, the description about the substitution position of each substituent is omitted, and the structural formula of the compound in each step is expressed in the form of a free acid.
First, equation (4)

[In Formula (4), d, e, f, and g are each independently 0 or 1, and the sum total is 2-4. ]

A copper phthalocyanine sulfonic acid represented by As described above, the α-position substitution product derived from the raw material is by-produced in the copper phthalocyanine dye of the formula (1) used in the ink composition of the present invention. However, in the description of the production method, the main component β- It is described in the position substitution product.
The compound of formula (4) can be synthesized, for example, by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a phthalic acid derivative in the presence of a catalyst and a copper compound.
By changing the molar ratio of the reaction between the 4-sulfophthalic acid derivative and the phthalic acid derivative, the number of sulfo groups, that is, the number of d to g can be adjusted. As 4-sulfophthalic acid derivatives, 4-sulfophthalic acid, 4-sulfophthalic anhydride, 4-sulfophthalimide, 4-sulfophthalamide, 4-sulfophthalonitrile, 4 or 5-sulfo-2-cyanobenzamide and 5-sulfo- 1,3-diiminoisoindoline or a salt thereof. Of these, 4-sulfophthalic acid or a salt thereof is usually preferred. Examples of the phthalic acid derivative include phthalic acid, phthalic anhydride, phthalimide, phthalamide, phthalonitrile, 2-cyanobenzamide and 1,3-diiminoisoindoline or salts thereof. However, in the case of 4-sulfophthalic acid, phthalic acid, 4-sulfophthalic anhydride, phthalic anhydride, 4-sulfophthalimide, phthalimide, 4-sulfophthalamide and phthalamide, addition of urea is essential. The amount of urea used is 5 to 100 times the molar amount of the total number of moles of 4-sulfophthalic acid derivative and phthalic acid derivative.

  The reaction is usually carried out in the presence of a solvent. As the solvent, an organic solvent having a boiling point of usually 100 ° C. or higher, more preferably 130 ° C. or higher is used. For example, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, trichlorobenzene, chloronaphthalene , Nitrobenzene, quinoline, sulfolane, urea and the like. The amount of the solvent used is 1 to 100 times the total amount of the 4-sulfophthalic acid derivative and the phthalic acid derivative.

  Examples of the catalyst include 1,8-diazabicyclo [5.4.0] -7-undecene, ammonium molybdate and boric acid. The amount added is 0.001 to 1 times the mol of the total number of moles of the 4-sulfophthalic acid derivative and the phthalic acid derivative.

  Examples of copper compounds include copper halides, carboxylates, sulfates, nitrates, acetylacetonates, carbonyl compounds, complexes, and the like. Examples thereof include copper chloride and copper bromide. The usage-amount of a copper compound is 0.15-0.35 times mole with respect to the total number-of-moles of 4-sulfophthalic acid derivative or 4-sulfophthalic acid derivative, and (unsubstituted) phthalic acid derivative.

  The reaction temperature is usually 100 to 290 ° C, preferably 130 to 270 ° C. Moreover, although reaction time changes with reaction temperature, it is 1 to 8 hours normally. After completion of the reaction, it is obtained in the form of copper phthalocyanine sulfonic acid or a salt thereof by filtration, salting out (or aciding out) and drying. In order to obtain a free acid, for example, acid precipitation may be performed. In addition, in order to obtain a salt, when salting out or a desired salt cannot be obtained by salting out, for example, a normal salt exchange method in which a desired organic or inorganic base is added to a free acid is used. That's fine.

  Moreover, the compound in which d, e, f, and g in Formula (4) are represented by 1 is synthesized by the method described in Patent Document 10, and 4-sulfophthalic acid (1 mol), copper chloride in a sulfolane solvent. By reacting (II) (0.3 mol), ammonium phosphomolybdate (0.003 mol), urea (6 mol), and ammonium chloride (0.5 mol) at 180 ° C. for 6 hours, the above formula (5) The copper phthalocyanine sulfonic acid represented by these is obtained. The reactivity varies depending on the type and amount of 4-sulfophthalic acid derivative, copper compound, solvent, catalyst, etc., and is not limited to the above.

The copper phthalocyanine sulfonic acid represented by the formula (4) or a salt thereof corresponds to the raw material used by reacting a chlorinating agent in a solvent such as an organic solvent, sulfuric acid, fuming sulfuric acid, or chlorosulfonic acid. Copper phthalocyanine sulfonic acid chloride is obtained. The chlorinating agent is preferably used in excess relative to the sulfo group of copper phthalocyanine sulfonic acid or a salt thereof, and is about 1 to 15 times, preferably 1.5 times or more, in molar ratio to the sulfo group. Examples of the organic solvent used in the reaction include, but are not limited to, benzene, toluene, nitrobenzene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide and the like. Examples of the chlorinating agent include, but are not limited to, chlorosulfonic acid, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like. Further, the copper phthalocyanine dye or its salt (I) used in the ink composition of the present invention is partially composed of impurities chlorinated in the phthalocyanine nucleus and a dye having a partially unreacted sulfo group in the reaction product. It may be mixed.
Although reaction conditions differ with the reactivity of the chlorinating agent to be used, they are 0-150 degreeC normally, and reaction time is 1 to 20 hours.

Next, the obtained copper phthalocyanine sulfonic acid chloride and the primary organic amine or ammonia and base corresponding to R ₁ are usually pH 8 to 12, usually 0 in a solvent such as organic solvent, water solvent, water-organic solvent mixed solvent. Sulfamoyl copper phthalocyanine is obtained by reacting at ˜70 ° C., usually for 1 to 20 hours. Examples of the organic solvent used include, but are not limited to, acetonitrile, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine and the like. The base may be an organic base or an inorganic base. Examples of the organic base include triethylamine and pyridine. Examples of the inorganic base include metal carbonates such as potassium carbonate and sodium carbonate, potassium hydroxide, and hydroxide. Although metal hydroxides, such as sodium, are mentioned, it is not limited to these. It is also possible to use a primary organic amine or ammonia corresponding to R ₁ as a base, and in this case, if the primary organic amine or ammonia corresponding to R ₁ is used in excess (more than 2 times the theoretical amount of mole). good.

  Further, the formula (5) corresponding to the sulfonylurea group of the obtained sulfamoyl copper phthalocyanine and copper phthalocyanine dye or salt (I)

[Wherein R ₃ , R ₄ , A, B, X, Y and Z have the same meaning as described above. R ₅ represents a phenyl group or a lower alkyl group. ]

The copper phthalocyanine dye or its salt (I) used in the ink composition of the present invention is obtained by reacting the carbamate compound represented by formula (1) with the sulfamoyl copper phthalocyanine by 1 to 8 moles. The amount of the carbamate compound used varies depending on the number of introduced sulfonylurea groups and the reactivity of the carbamate compound, and may be adjusted as appropriate. Usually, the reaction is carried out in an organic solvent, water and a water-organic solvent mixed system, and a base is required for the reaction. Examples of the organic solvent that can be used include, but are not limited to, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, dioxane, N-methylpyrrolidone, and the like. . The base may be an organic base or an inorganic base. Examples of the organic base include 1,8-diazabicyclo [5.4.0] -7-undecene, triethylamine, pyridine and the like. Examples of the inorganic base include: Examples thereof include metal carbonates such as potassium carbonate and sodium carbonate, and metal hydroxides such as potassium hydroxide and sodium hydroxide, but are not limited thereto.
The reaction conditions are usually 0 to 120 ° C, preferably 20 to 80 ° C. Moreover, although reaction time changes with reaction conditions, it is 1 to 40 hours normally.

  Next, the manufacturing method of the carbamate compound represented by Formula (5) is demonstrated. For example, the formula (6)

[In Formula (6), R < ₃ >, R < ₄ >, A, B, X, Y, and Z represent the same meaning as the above. ]

The carbamate compound represented by the formula (5) is obtained by reacting the amine represented by the formula (II) and the chloroformate in a water solvent, an organic solvent, or a water-organic solvent mixed system in the presence of a base. Examples of the organic solvent that can be used include, but are not limited to, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, N-methylpyrrolidone, chloroform, dichloromethane, toluene and the like. It is not a thing. The base may be an organic base or an inorganic base. Examples of the organic base include 1,8-diazabicyclo [5.4.0] -7-undecene, triethylamine, pyridine and the like. Examples of the inorganic base include Examples thereof include metal carbonates such as potassium carbonate and sodium carbonate, and metal hydroxides such as potassium hydroxide and sodium hydroxide, but are not limited thereto. As the chloroformate, methyl ester, ethyl ester, phenyl ester and the like can be easily obtained, but considering the reaction with sulfamoyl metal phthalocyanine in the next step, phenyl ester having high reactivity is most preferable.

  Moreover, the amine represented by Formula (6) is manufactured as follows. For example, amines corresponding to X, alcohols or thiols, usually 0.95 to 1.1 mol and 2,4,6-trichlorotriazine (cyanuric chloride) 1 mol in water, usually pH 3 to 7, usually 5 The primary condensate is obtained by reacting at -40 ° C, usually 2-12 hours. Next, secondary condensation is carried out by reacting amines, alcohols or thiols corresponding to Y, usually 0.95 to 1.1 mol, usually pH 4 to 10, usually 5 to 80 ° C., usually 0.5 to 12 hours. Get things. Then, usually by reacting 1 to 50 moles of amines, alcohols or thiols corresponding to the crosslinking group at pH 9 to 12, usually 20 to 90 ° C., usually 0.5 to 8 hours, the formula (6) An amine is obtained. The order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.

In addition, the copper phthalocyanine dye or salt (I) used in the ink composition of the present invention has some impurities in which the phthalocyanine ring (Pc) forms a dimer or trimer via a divalent linking group. It may be produced and mixed in the reaction product, and a plurality of linking groups present at that time may be the same or different. Examples of the divalent linking group include a sulfonyl group (—SO ₂ —) and —SO ₂ —NH—SO ₂ —. The linking group may be a group formed by combining them.

  The copper phthalocyanine dye or salt (I) thus obtained can be separated by filtration or the like after aciding out or salting out. For example, salting out is preferably performed in the range of acidic to alkaline, preferably pH 1-11. Although the temperature at the time of salting out is not specifically limited, It is preferable to salt out by adding salt etc. after heating to 40-80 degreeC normally, Preferably it is 50-70 degreeC.

  The phthalocyanine dye represented by the formula (1) or (2) used in the ink composition of the present invention synthesized by the above method can be obtained in the form of a free acid or a salt thereof. In order to obtain a free acid, for example, acid precipitation may be performed. In addition, in order to obtain a salt, when salting out or a desired salt cannot be obtained by salting out, for example, a usual salt exchange method in which a desired organic or inorganic base is added to a free acid is employed. That's fine.

  Details of the method for producing the copper phthalocyanine dye of formula (2) or a salt thereof used in the ink composition of the present invention are described in Patent Document 5 or Patent Document 10.

The cyan composition of the present invention contains the copper phthalocyanine dye of the formula (1) or a salt thereof (I) and the copper phthalocyanine dye of the formula (2) or a salt thereof (II) produced by the above method, Although prepared using water as a medium, when this ink is used as an ink for inkjet recording, Cl ⁻ and SO which also form inorganic salts contained in the base of copper phthalocyanine dye or salts (I) and (II) thereof. It is preferable that the content of anions such as ₄ ²⁻ is small, and the standard of the content is 5% by mass or less, preferably 3% as the total content of Cl ⁻ and SO ₄ ^{2− in} the raw material of the phthalocyanine dye mixture. It is 1 mass% or less in an ink, More preferably, it is 1 mass% or less. In order to produce a copper phthalocyanine dye or a salt thereof containing a small amount of Cl ⁻ and SO ₄ ²⁻ , for example, a conventional method using a reverse osmosis membrane or a dried product or wet cake of a copper phthalocyanine dye or a salt thereof in a mixed solvent of alcohol and water. And desalting by a method such as stirring and filtration. The alcohol used is a lower alcohol having 1 to 4 carbon atoms, preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol, ethanol or 2-propanol. Further, in the desalting treatment with alcohol, a method of heating to near the boiling point of the alcohol used and then cooling to desalinate can be employed. The content of Cl ⁻ and SO ₄ ²⁻ is measured, for example, by ion chromatography.

  When the ink composition of the present invention is used as an ink for ink jet recording, the content of a heavy metal (ion) such as zinc or iron, a metal (cation) such as calcium or silica contained in a copper phthalocyanine dye or a salt thereof is included. It is preferable to use a small amount (excluding copper contained in the phthalocyanine skeleton). The standard of the content is, for example, about 500 ppm or less for each of heavy metals (ions) such as zinc and iron and metals (cations) such as calcium and silica in a purified and dried product of a copper phthalocyanine dye or a salt thereof. The contents of heavy metals (ions) and metals (cations) are measured by ion chromatography, atomic absorption method or ICP (Inductively Coupled Plasma) emission analysis.

  In the ink composition of the present invention, the copper phthalocyanine dye or a salt thereof is usually contained in an amount of 0.1 to 10% by mass, preferably 0.5 to 8% by mass in combination of (I) and (II). The ink having a low concentration usually contains 0.1 to 2.5% by mass of (I) and (II).

  Each ratio of the copper phthalocyanine dye or its salt (I) and (II) is preferably in the range of (I) :( II) = 10: 90 to 80:20, and (I) :( II) = More preferably, it is in the range of 30:70 to 60:40.

  The ink composition of the present invention is prepared using water as a medium. If necessary, the ink composition of the present invention further contains a water-soluble organic solvent within a range that does not impair the effects of the present invention. Water-soluble organic solvents are used as dye solubilizers, drying inhibitors (wetting agents), viscosity modifiers, penetration enhancers, surface tension modifiers, antifoaming agents, and the like. Other ink preparation agents include, for example, antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, UV absorbers, viscosity adjusters, dye solubilizers, antifading agents, emulsion stabilizers, surface tension adjusters, Well-known additives, such as an antifoamer, a dispersing agent, a dispersion stabilizer, are mentioned. The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0 to 15% by mass, based on the entire ink. Is good. The remainder other than the above is water.

  Examples of water-soluble organic solvents that can be used to prepare the ink composition of the present invention include C1-C4 such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. Carboxylic acid amides such as alkanol, N, N-dimethylformamide or N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethyl Heterocyclic ketones such as hexahydropyrimido-2-one, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as keto alcohol, tetrahydrofuran, dioxane, ethylene glycol, 1 , 2- or 1,3-propylene Recall, 1,2- or 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. C6) Monomers, oligomers or polyalkylene glycols or thioglycols having alkylene units, polyols (triols) such as glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or Diethylene glycol monoethyl ether or triethylene glycol monomethyl ether or triethylene glycol monoethyl Polyhydric alcohols (C1 -C4) alkyl ethers such as ether, gamma-butyrolactone or dimethyl sulfoxide and the like.

  Preferable examples of the water-soluble organic solvent include mono- or polyhydric alcohols having 3 to 8 carbon atoms and 2-pyrrolidone optionally having alkyl substitution of 1 to 3 carbon atoms. Having 2 to 3 is preferable. Specifically, isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, butanol, etc., more preferably isopropanol, glycerin, diethylene glycol, 2-pyrrolidone, Butyl carbitol, N-methyl-2-pyrrolidone. These water-soluble organic solvents are used alone or in combination.

  Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzthiazole, nitrile, pyridine, 8- Oxyquinoline, benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate And brominated indanone compounds, benzyl bromacetate compounds, inorganic salt compounds, and the like. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide, and examples of the inorganic salt compound include anhydrous sodium acetate. Examples of the isothiazoline-based compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Is mentioned. Other antiseptic / antifungal agents include sodium sorbate sodium benzoate and the like (for example, Proxel GXL (S), Proxel XL-2 (S), etc., manufactured by Avecia).

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. And carbonates.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like. Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, and benzoxazole compounds. In addition, a compound that absorbs ultraviolet rays and emits fluorescence, a so-called fluorescent brightener can also be used.

  Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

  Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like.

  The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like.

  Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, rosin acid soap, castor oil sulfate Examples thereof include ester salts, lauryl alcohol sulfates, alkylphenol phosphates, alkyl phosphates, alkylallyl sulfonates, and diethylsulfosuccinates. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl Ethers such as ether, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate Esters such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-o Acetylene glycols such as tin-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol (for example, Surfinol 104, 104PG50, 82, 465, Olphine STG, etc. manufactured by Nissin Chemical), etc. Is mentioned. These ink preparation agents are used alone or in combination. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m. The viscosity of the ink of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.

  As the antifoaming agent, a fluorine-based or silicone-based compound is used as necessary.

  The ink composition of the present invention can be obtained by dissolving each drug in water, but the dissolution order is not particularly limited. The water to be used is preferably one having few impurities such as ion exchange water or distilled water. After dissolution, if necessary, microfiltration may be performed using a membrane filter to remove impurities. When used as ink for an ink jet printer, it is preferable to perform microfiltration. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 microns, preferably 0.8 to 0.2 microns.

  The ink composition of the present invention can be used not only for forming a single color image but also for forming a full color image. In order to form a full-color image, it is also used as an ink set with magenta ink, yellow ink, and black ink. Furthermore, in order to form a higher-definition image, the ink set is used in combination with light magenta ink, blue ink, green ink, orange ink, dark yellow ink, gray ink, and the like.

  Various yellow ink pigments can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone as coupling components (hereinafter referred to as coupler components); azomethine dyes, benzylidene dyes and monomethine oxonol dyes There are quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, acridinone dyes and the like.

  Various types of magenta ink can be used. For example, arylazo dyes having phenols, naphthols, anilines, etc. as coupler components; azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, oxonol dyes, etc. Examples thereof include methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure. Examples of applicable black pigments include disazo, trisazo, and tetraazo dyes, and carbon black dispersions.

  The ink composition of the present invention can be used for recording methods such as printing, copying, marking, writing, drawing, stamping, and the like, and is particularly suitable for use in ink jet printing.

  In the ink jet recording method of the present invention, energy is supplied to the ink prepared as described above, and a known image receiving material, that is, plain paper, resin-coated paper, ink jet exclusive paper, glossy paper, glossy film, electrophotographic co-paper, fiber Images are formed on fabrics (such as cellulose, nylon and wool), glass, metal, ceramics, and leather.

  When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing for applying the polymer latex to the recording material may be before, after, or simultaneously with the application of the colorant. Alternatively, it may be in an ink or may be used as a liquid material of a polymer latex alone.

  The bronze phenomenon suppressing method of the present invention is performed using the ink adjusted as described above, but may be used in combination with other bronze suppressing methods such as those described in Patent Documents 1 to 4, for example. I do not care.

  The colored product of the present invention is colored with the above-described aqueous ink composition of the present invention. Examples of materials that can be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and base materials for color filters. The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. In the ink receiving layer, inorganic fine particles capable of absorbing pigments in inks such as porous silica, alumina sol, and special ceramics are impregnated or coated with the above-mentioned base material with a cationic polymer, for example, polyvinyl alcohol or polyvinylpyrrolidone. It is provided by coating on the surface of the substrate together with a hydrophilic polymer such as. Those provided with such an ink-receiving layer are usually referred to as inkjet paper (film), glossy paper (film) and the like. Of these, ozone gas and other gases that have an oxidizing action in the air are considered to be easily affected by inorganic fine particles that can absorb pigments in inks such as porous silica, alumina sol, and special ceramics. This type of inkjet paper is coated on the surface of the material. For example, typical commercial products include Pictorico (manufactured by Asahi Glass Co., Ltd.), professional photo paper, super photo paper, matte photo paper (all Also made by Canon Inc.), photo paper <gloss>, photo matte paper (both made by Seiko Epson Corp.), premium gloss film, photo paper (both made by Hewlett-Packard Japan), photo-like QP (Manufactured by Konica Corporation), high-grade coated paper, photographic glossy paper (all manufactured by Sony Corporation), etc.Of course, plain paper can also be used.

  The colored body of the present invention is obtained by coloring a material to be colored with the ink using an inkjet printer. The colorant is not particularly limited as long as it is an article that can be colored by the recording material and other ink jet printers.

  In order to record on the recording material by the ink jet recording method of the present invention, for example, a container containing the above-mentioned ink may be set at a predetermined position of the ink jet printer and recorded on the recording material by an ordinary method. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating.

  The ink composition according to the present invention does not precipitate or separate during storage. Further, when the ink according to the present invention is used in ink jet printing, the ejector (ink head) is not blocked. The ink according to the present invention does not cause changes in physical properties even under constant recirculation for a relatively long time by a continuous ink jet printer or intermittent use by an on-demand ink jet printer.

  The ink composition of the present invention has a clear cyan color. Although it is generally known that a high-quality recorded image with less graininess can be obtained by using a set of dark and light cyan inks, the ink composition of the present invention is further divided into dark cyan and light cyan, respectively. By using it, it is possible to avoid the problem of bronzing, which tends to be a problem with dark cyan, and the problem of lowered ozone resistance, which is likely to be a problem with light cyan. In addition, when used with other yellow, magenta, and other inks such as green, red, orange, and blue as necessary, it is possible to develop a color tone in a wide visible region, and it has excellent ozone resistance and light resistance. Recording material that is excellent also in water resistance and water resistance.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the text, “parts” and “%” are based on mass unless otherwise specified.

Example 1
(1) In a four-necked flask, 49.2 parts of 4-sulfophthalic acid (manufactured by Pilot, 50% aqueous solution, containing 20% 3-sulfophthalic acid) was added and stirred, and 17.7 parts of 25% aqueous sodium hydroxide solution was added. In addition, the pH was adjusted to 0.8 to 1.0. 126 parts of sulfolane was added to this, and it heated gradually, and heated up to 160 degreeC, distilling off water. After cooling to 100 ° C., 3.83 parts of copper (II) chloride dihydrate, 0.47 part of ammonium molybdate and 37.1 parts of urea were added, and the mixture was stirred at 180 ° C. for 2 hours and at 200 ° C. for 4 hours. . After the reaction solution was cooled to 40 ° C., the target product was filtered with Nutsche and washed with 400 parts of methanol. Subsequently, 300 parts of water was added to the obtained wet cake, adjusted to pH 11 with a 48% aqueous sodium hydroxide solution, and stirred at 80 ° C. for 1 hour. While stirring, 35% hydrochloric acid aqueous solution was added to adjust the pH to 3, and 80 parts of sodium chloride was gradually added thereto. The precipitated crystals were collected by filtration and washed with 150 parts of a 20% aqueous sodium chloride solution to obtain 90 parts of a wet cake. Subsequently, 210 parts of methanol was added and stirred for 1 hour, and the precipitated crystals were separated by filtration, washed with 300 parts of a 70% aqueous methanol solution and dried, and the ratio in which the sulfo group was substituted at the β-position of the following formula (7) Of copper phthalocyanine tetrasulfonic acid tetrasodium salt (19.1 parts) was obtained as blue crystals. λmax: 629 nm (in weakly alkaline aqueous solution). When the obtained phthalocyanine compound (mixture) was decomposed into a phthalic acid derivative with nitric acid was analyzed by NMR, the ratio of the 4-sulfophthalic acid derivative to the 3-sulfophthalic acid derivative was 80:20.

(2) Gradually charge 9.8 parts of copper phthalocyanine tetrasulfonic acid tetrasodium salt (compound of formula (7)) obtained in (1) at 60 ° C. or lower with stirring in 79 parts of chlorosulfonic acid, The reaction was carried out at 4 ° C. for 4 hours. Next, the reaction solution was cooled to 80 ° C., 47.6 parts of thionyl chloride was added dropwise over 30 minutes, and the reaction was performed at 80 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 700 parts of ice water, the precipitated crystals are filtered, washed with 200 parts of ice-cold 2% hydrochloric acid aqueous solution, and copper phthalocyanine tetrasulfonic acid chloride of the following formula (8). Of wet cake was obtained. This copper phthalocyanine tetrasulfonic acid chloride has a partially unreacted sulfo group. It was confirmed by high performance liquid chromatography after quenching the obtained copper phthalocyanine tetrasulfonyl chloride with a large excess of isopropylamine.
In the formula (8), e and f are average values obtained from the area ratio of high performance liquid chromatography, and the values are h = 0.2 and i = 3.8.

(3) In 400 parts of ice water, 35.2 parts of a wet cake of the copper phthalocyanine tetrasulfonic acid chloride (compound of formula (8)) obtained in (2) was added and suspended by stirring at 5 ° C or lower. While maintaining the temperature at 10 ° C. or lower, 28% ammonia water was added to adjust the pH to 10.5 to 11.0 and held for 2 hours. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour, kept at the same temperature for 2 hours, and further kept at 30 ° C. for 2 hours. The liquid volume at this time was 600 parts. The temperature of the reaction liquid was raised to 50 ° C., 30 parts of sodium chloride (20% to the liquid) was added and stirred for 30 minutes, then filtered, washed with 100 parts of water, washed with 100 parts of 50% aqueous ethanol, dried, Copper phthalocyanine tetrasulfamoyl of formula (9) was obtained as 8.9 parts of blue crystals.
J and k in the formula (9) are average values obtained from ion chromatography or the like, and the values were j = 1.2 and k = 2.8.

(4) 1.1 parts of Lipar OH (trade name, anionic surfactant, manufactured by Lion Corporation) and 36.8 parts of cyanuric chloride were added to 150 parts of ice water and stirred for 30 minutes. Next, 58.0 parts of aniline-2,5-disulfonic acid monosodium salt was added, the pH was maintained at 2.7 to 3.0 while adding a 25% aqueous sodium hydroxide solution, and the mixture was maintained at 10 to 15 ° C. for 2 hours. Reaction was performed at 25-30 degreeC for 1 hour. Next, after cooling the reaction solution to 15 ° C. or lower, 9.1 parts of morpholine was added dropwise while maintaining the pH at 7.0 to 8.0. After dropping, the pH was maintained at 7.0 to 8.0 while adding a 25% aqueous sodium hydroxide solution, and the reaction was carried out at 20 to 30 ° C. for 1 hour. Next, 12.5 parts of 2-aminoethanethiol was added, the pH was maintained at 7.0 to 8.0 while adding a 25% aqueous sodium hydroxide solution, and the reaction was performed at 30 to 40 ° C. for 3 hours. The liquid volume was adjusted to 750 parts, and 150 parts of sodium chloride was added to precipitate crystals. The precipitated crystals were collected by filtration and washed with 250 parts of a 20% aqueous sodium chloride solution to obtain 296 parts of a wet cake. 296 parts of the obtained wet cake was put into 1000 parts of methanol, suspended and stirred at 50 ° C. for 1 hour, filtered, washed with methanol, and dried to obtain 170 parts of white powder. 126 parts of the white powder is put into 1500 parts of water, adjusted to pH 9.0-10.0 with 25% aqueous sodium hydroxide solution, the reaction solution is cooled to 20 ° C. or less, and 47.5 parts of phenyl chloroformate are added. The reaction was carried out at 20-30 ° C. while maintaining pH 7.0-8.0 while adding 25% aqueous sodium hydroxide solution. The liquid volume was adjusted to 1800 parts, and 360 parts of sodium chloride was added to precipitate crystals. The precipitated crystals were collected by filtration and washed with a 20% aqueous sodium chloride solution to obtain 306 parts of a wet cake. The obtained wet cake was vacuum dried at 30 ° C. to obtain 129 parts of the compound of the formula (10).

(5) 2.2 parts of the copper phthalocyanine tetrasulfamoyl (compound of formula (9)) obtained in (3) was put into 30 parts of dimethylformamide and dissolved by heating to 50 ° C. The solution was cooled to 20 ° C., 1.40 parts of the compound of the formula (10) obtained in (4) was added, and the mixture was stirred for 30 minutes. To this solution, a solution prepared by dissolving 0.38 part of 1,8-diazabicyclo [5,4,0] -7-undecene in 1.9 parts of dimethylformamide was added dropwise and reacted overnight. The reaction solution was added dropwise to 100 parts of 2-propanol to precipitate crystals. The precipitated crystals were collected by filtration and washed with 100 parts of 2-propanol to obtain 30.3 parts of a wet cake. 30.3 parts of the obtained wet cake was put into 100 parts of water, lithium hydroxide was added and completely dissolved at pH 11.0 to 10.5. The liquid volume was adjusted to 300 parts, 30 parts of lithium chloride was added, the pH was adjusted to 1.0 with 35% hydrochloric acid, and crystals were precipitated. The precipitated crystals were collected by filtration and washed with 50 parts of a 20% aqueous lithium chloride solution to obtain 22.5 parts of a wet cake. The obtained wet cake was put into 200 parts of 2-propanol, 60 parts of water was added, and the mixture was stirred and suspended at 60 ° C. for 1 hour, followed by filtration, washing with methanol, and drying. 4.3 parts of a copper phthalocyanine dye were obtained. As a result of analysis, x = 1.2, y = 1.72, z = 1.08, and the maximum absorption wavelength (λmax) in water was 616 nm.

Example 2 (Ink evaluation)
(A) Preparation of ink Each component described in Table 12 below was mixed and dissolved to obtain the ink of the present invention. Subsequently, impurities were removed by filtering with a 0.45 μm membrane filter (manufactured by Advantech). The water used was ion exchange water. Further, water and caustic soda (pH adjuster) were added so that the pH of the ink was 9 to 10 and the total amount was 100 parts. The copper phthalocyanine dye or its salt (I) is the dye obtained in Example 1 above, and the copper phthalocyanine dye or its salt (II) is the dye of the specific compound example 154 of Patent Document 11 (the following formula (Represented by (12)).

Table 12
Copper phthalocyanine dye obtained in Example 1 3.5 parts Dye of specific compound example 154 of Patent Document 11 3.5 parts Glycerin 8.0 parts Urea 8.0 parts N-methyl-2-pyrrolidone 7.0 Parts IPA (isopropyl alcohol) 5.0 parts butyl carbitol 3.0 parts Surfinol 104PG50 (trade name: manufactured by Nissin Chemical) 0.2 parts total 100.0 parts

  As Comparative Example 1, an ink was prepared with the same composition as in Table 10 except that 7.0 parts of the copper phthalocyanine dye obtained in Example 1 and 0 parts of the dye of the specific compound example 154 of Patent Document 11 were used.

  As Comparative Example 2, an ink was prepared with the same composition as in Table 10 except that 0 part of the copper phthalocyanine dye obtained in Example 1 and 7.0 part of the dye of the specific compound example 154 of Patent Document 11 were used.

(B) Inkjet printing Using an inkjet printer (trade name: PIXUS ip4100 manufactured by Canon Inc.), exclusive film A (photo glossy film HG201 manufactured by Canon Inc.), dedicated film B (PICTORICA PRO Glossy Film PPF-A4 manufactured by PICTORICA) Inkjet recording was performed on the seeds. The dedicated paper A and the dedicated paper B used in the test are recording media having an ink image receiving layer containing white inorganic pigment particles on a support.
At the time of printing, an image pattern was prepared so that gradations with several levels of reflection density were obtained, and a halftone printed matter was obtained. In the measurement of the light resistance test and the ozone resistance test, the measurement was performed by using the gradation portion where the reflection density D value of the printed material before the test was closest to 1.0. The bronze phenomenon was also evaluated using the same part.

(C) Evaluation of recorded image Hue evaluation The hue of the recorded image is determined by measuring a ^* and b ^* values when L ^{* of} the printed material is in the range of 40 to 80 by measuring the color of the recording paper using a color measuring system (GRETAG SPM50: manufactured by GRETAG). Measured color. Evaluation was carried out in three stages, with preferable a ^* values defined as -60 to -20 and b ^* values defined as -60 to -20.
○: Both a ^* and b ^* values exist in a preferred region. Δ: Only one of a ^* and b ^* values exists in a preferred region. ×: Both a ^* and b ^* values exist outside a preferred region.

2. Light resistance test An air layer and a glass plate with a thickness of 2 mm are placed on a test piece of a recorded image, and a xenon weather meter (Model Ci4000 manufactured by ATLAS) is used, and the temperature in the bath is 24 ° C. and the humidity is 0.36 W / square meter. Irradiation was performed at 60% RH for 50 hours. After the test, the reflection density was measured using a color measurement system. After the measurement, the dye residual ratio was calculated by (reflected density after test / reflected density before test) × 100 (%) and evaluated in three stages.
○: Residual rate 70% or more Δ: Residual rate 50-70%
×: Residual rate less than 50%

3. Ozone resistance test The test piece of the recorded image was allowed to stand for 3 hours at an ozone concentration of 40 ppm, a bath temperature of 24 ° C., and a humidity of 60% RH using an ozone weather meter (model OMS-H manufactured by Suga Test Instruments Co., Ltd.). After the test, the reflection density was measured using the color measurement system. After the measurement, the dye residual ratio was calculated by (reflected density after test / reflected density before test) × 100 (%) and evaluated in four stages.
◎: Residual rate 85% or more ○: Residual rate 70% or more, less than 85% △: Residual rate 40% or more, less than 70% ×: Residual rate less than 40%

4). Humidity resistance test The test piece of the recorded image was left for 3 days at a temperature of 50 ° C. and a humidity of 90% RH using a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.). After the test, the bleeding of the test piece was visually evaluated in three stages.
○: No blurring is observed Δ: Slight blurring is observed ×: Large blurring is observed

4). Evaluation of Bronze Phenomenon The test piece of the recorded image was measured for the glossiness of 60 ° light entering the company using a gloss meter (model PG-1M manufactured by Nippon Denshoku Co., Ltd.). The difference in gloss before printing and after printing was calculated and evaluated in three stages according to the following criteria.
○: Glossiness difference is less than 5 Δ: Glossiness difference is 5 or more and less than 15 ×: Glossiness difference is 15 or more

Table 13 (special paper A) and 148 show the hue evaluation, light resistance test result, ozone resistance test result, and moisture resistance test result of the recorded image of the ink (C-1) using the compound obtained in Example 1. (Dedicated paper B).

Table 13
Ink evaluation result: Dedicated film A
Ink number Hue Light resistance Ozone resistance Moisture resistance Bronze phenomenon Example 2 ○ ○ ◎ ○ △
Comparative Example 1 ○ ○ ◎ ○ ×
Comparative Example 2 ○ ○ ◎ ○ ×

Table 14
Ink evaluation result: Dedicated film B
Ink number Hue Light resistance Ozone resistance Moisture resistance Bronze phenomenon Example 2 ○ ○ ◎ ○ ○
Comparative Example 1 ○ ○ ◎ ○ △
Comparative Example 2 ○ ○ ◎ ○ △

As is apparent from Tables 13 and 14, the ink composition of the present invention is excellent in hue, excellent in light resistance, ozone resistance and moisture resistance, and further, the bronzing phenomenon is clearly improved.

Claims (22)

An ink composition comprising a copper phthalocyanine dye or a salt thereof having a sulfonylurea group as a substituent, and a copper phthalocyanine dye or a salt thereof having an alkylsulfonyl group as a substituent. The mixing ratio of the copper phthalocyanine dye or a salt thereof having a sulfonylurea group as a substituent and the copper phthalocyanine dye or a salt thereof having an alkylsulfonyl group as a substituent is 10:90 to 80:20 by mass ratio. The ink composition according to 1. 2. The ink composition according to claim 1, wherein the ratio of the dye mixture contained in the ink composition is 0.5 to 8% by mass when the concentration is high, and 0.1 to 2.5% by mass when the concentration is low. . Following formula (Q)

Wherein R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, A represents a bridging group, B represents a heteroatom, and when B is a divalent heteroatom, R ₄ does not exist. Adjacent R ₃ , R ₄ , A and B may be connected to each other to form a ring, Z represents a nitrogen atom or a substituted carbon atom, and X and Y independently represent a halogen atom or a hydroxyl group. , Sulfo group, carboxyl group, amino group, substituted or unsubstituted nitrogen-containing heterocyclic group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkoxy group, substituted or unsubstituted allyloxy Substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or Unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted An alkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio group; And at least one of X and Y Have a substituent represented by the ionic hydrophilic group is a group having as a substituent.), The following equation (q)

-SO ₂ R ₅ (q)

(Wherein R ₅ represents an alkyl group optionally having one or more ionic hydrophilic groups as a substituent), a copper phthalocyanine dye having no substituent or a salt thereof, The ink composition according to claim 1, comprising a copper phthalocyanine dye or a salt thereof having a substituent represented by the formula (q) and not having a substituent represented by the formula (Q). When the copper phthalocyanine dye or salt thereof having a sulfonylurea group as a substituent is (I) and the copper phthalocyanine dye or salt thereof having an alkylsulfonyl group as a substituent is (II), (I) is represented by the following formula (1)

(Wherein CuPc represents a copper phthalocyanine skeleton, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group, An aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, A represents a bridging group, B represents a heteroatom, and B represents a divalent atom. In the case of a hetero atom, R ₄ does not exist, adjacent R ₃ , R ₄ , A and B may be connected to each other to form a ring, Z represents a nitrogen atom or a substituted carbon atom. Y is independently a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a substituted or unsubstituted nitrogen-containing heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloal Coxi group, substituted or unsubstituted allyloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or Unsubstituted cycloalkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted Dialkylamino group, substituted or unsubstituted alkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted aralkylthio group A substituted or unsubstituted alkenylthio group In addition, at least one of X and Y is a group having an ionic hydrophilic group as a substituent, a = 0 to 2, b = 0 to 4, c = 0 to 3, and a + b + c = 2-4.)
And (II) is represented by the following formula (2):

(In the formula, R _{5 to} R ₈ each independently represents a substituted or unsubstituted alkyl group, provided that at least one of R _{5 to} R ₈ has an ionic hydrophilic group as a substituent.)
The ink composition according to any one of claims 1 to 4, wherein the ink composition is represented by: The copper sulfophthalocyanine dye of (I) or a salt thereof, when oxidized, 60% or more of the obtained sulfophthalic acid derivative is a 4-sulfophthalic acid derivative in a molar ratio. The ink composition according to one item. (I) is the following formula (3)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , X, Y, Z represent the same meaning as in the formula (1). A, b, and c also have the same meaning as in the formula (1). To express.)
The ink composition according to any one of claims 1 to 6, represented by: R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, C1 to C8 alkyl groups (from the group consisting of sulfo group, carboxyl group, hydroxyl group, alkoxy group, dialkylamino group, acetylamino group, cyano group and arylthio group) A C3 to C7 cycloalkyl group (which may be substituted with a substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a dialkylamino group and an acetylamino group) or The ink composition according to any one of claims 1 to 7, which is an aralkyl group (which may be substituted with a sulfo group). 9. A is alkylene, cycloalkylene, and arylene, B is a sulfur atom and a nitrogen atom, and R ₄ is a hydrogen atom (when B is a sulfur atom, R ₄ does not exist). The ink composition according to any one of the above. The ink composition according to any one of claims 1 to 9, wherein the substituent of the substituted carbon atom in Z is a halogen atom, a carboxyl group, or a formyl group. X and Y are each independently a chlorine atom, hydroxyl group, amino group, carboxyl group, sulfo group, alkoxy group (sulfo group, carboxyl group, hydroxyl group, dialkylamino group, arylamino group, acetylamino group, alkoxy group, aryl 1 group selected from a group, a cyano group, a halogen atom and an arylthio group), a phenoxy group (sulfo group, carboxyl group, ureido group, alkyl group, alkoxy group, dialkylamino group, acetylamino group) A naphthoxy group (which may be substituted with one or more substituents selected from a sulfo group, a carboxyl group, an acetylamino group and an arylamino group) , Benzyloxy group (benzene nucleus may be substituted with sulfo group), phenethyloxy group (ben Nuclei may be substituted with sulfo groups), alkylamino groups (sulfo groups, carboxyl groups, hydroxyl groups, dialkylamino groups, arylamino groups, acetylamino groups, alkoxy groups, aryl groups, cyano groups, halogen atoms, arylthio groups. Anilino group (sulfo group, carboxyl group, ureido group, alkyl group, alkoxy group, hydroxyl group, dialkylamino group, acetylamino group, cyano group, nitro group, halogen atom, heterocyclic group) A naphthylamino group (sulfo group, carboxyl group, ureido group, alkyl group, alkoxy group, hydroxyl group, dialkylamino group, acetylamino group, cyano) One or more selected from a group, a nitro group, a halogen atom, and a heterocyclic group A benzylamino group (the benzene nucleus may be substituted with a sulfo group), a phenethylamino group (the benzene nucleus may be substituted with a sulfo group), an alkylthio group (a sulfo group, A carboxyl group or a hydroxyl group), an arylthio group (which may be substituted with one or more substituents selected from a sulfo group, a carboxyl group, a hydroxyl group and an alkyl group) and morpholine-4- The ink composition according to claim 1, wherein the ink composition is an yl group. R _{1 to} R ₄ are hydrogen, isopropyl group and hydroxyethyl group, A is ethylene, butylene and hexylene, B is a nitrogen atom or a sulfur atom (provided that B is a sulfur atom, R ₄ is not present) X is an anilino group which may have a hydroxyl group, a sulfo group, a carboxyl group and a nitro group, or a naphthylamino group which may have the same substituent as the anilino group, and Y is a sulfoethyl group, a methoxy group The dye or its salt of Claim 1 which is an amino group or morpholino group which may have a group, a hydroxyl group, a carboxymethyl group, and a hydroxyethyl group as a substituent, and Z is a nitrogen atom. R _{5 to} R ₈ are each independently an alkyl group having 2 to 5 carbon atoms (alkoxy group, hydroxyl group, carboxyl group, sulfo group, alkoxy group which may have a substituent, alkoxy which may have a substituent) 2. It may be substituted with one or more substituents selected from an alkoxy group, an amide group that may have a substituent, and a sulfonamide group that may have a substituent. The ink composition according to claim 12. R _{5 to} R ₈ are each independently substituted with one or two substituents selected from an alkyl group having 2 to 5 carbon atoms (a sulfo group, a hydroxyl group, and a sulfonamide group which may have a substituent). The ink composition according to any one of claims 1 to 13, which may be The ink composition according to any one of claims 1 to 14, wherein the maximum absorption wavelength in water in the visible light region of the copper phthalocyanine dye of (I) or a salt thereof is 608 to 620 nm. The ink composition according to any one of claims 1 to 15, wherein the copper phthalocyanine dye or salt thereof (I) accounts for 10 to 80% in a molar ratio in all the pigments in the ink composition. . The ink composition according to any one of claims 1 to 16, which is for inkjet recording. An ink jet recording method using the ink composition according to claim 17. A method for suppressing a bronze phenomenon using the ink composition according to any one of claims 1 to 18. 19. The ink jet recording method according to claim 18, wherein the recording material is an information transmission sheet. 21. The ink jet recording method according to claim 20, wherein the recording material is an information transmission sheet called an absorptive medium having a fine porous structure using white inorganic fine particles as an ink absorbing layer. The colored body colored with the method as described in any one of Claims 17-21.