JP4849873B2 - Phthalocyanine dye, ink, ink set, ink jet recording method using this ink or ink set, and colored body - Google Patents

Description

The present invention relates to a phthalocyanine dye, an ink, an ink set, an ink jet recording method using the ink or the ink set, and a colored body.

In recent years, a material for forming a color image has been mainly used as an image recording material. Specifically, an inkjet recording material, a thermal transfer type image recording material, a recording material using an electrophotographic system, a transfer type halogen, and the like. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. In addition, color filters are used in electronic parts such as LCDs and PDPs in displays and CCDs in photography equipment. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixing method and subtractive color mixing method are used to reproduce or record a full color image. In fact, there is no dye having an absorption characteristic that can realize the above-mentioned characteristics and can withstand various use conditions, and improvement is strongly desired.

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

For dyes used in inks suitable for such ink jet recording, the solvent has good solubility or dispersibility, high density recording is possible, hue is good, light, heat, It has durability against active gases in the environment (NOx, ozone and other oxidizing gases, SOx, etc.), excellent durability against water and chemicals, and fixability to recording materials. It is required that the ink does not bleed well, has excellent storability as an ink, has no toxicity, and can be obtained at low cost. In particular, it has a good cyan hue, is excellent in light resistance (durability against light), ozone resistance (durability against ozone gas) and moisture resistance (durability under high humidity), and is also called bronzing phenomenon (bronzing phenomenon) Cyan dyes that do not cause) are strongly desired. The bronze phenomenon refers to a phenomenon in which the dye becomes flakes on the surface of glossy paper or the like due to the association of the dye or poor ink absorption. When this phenomenon occurs, the glossiness, print quality, and print density are all inferior.

Typical skeletons of water-soluble cyan dyes used in inks suitable for ink jet recording are phthalocyanine and triphenylmethane. Typical phthalocyanine dyes reported and utilized most widely include phthalocyanine derivatives classified as A to J below.

A: C.I. I. Direct Blue 86, C.I. I. Direct Blue 87, C.I. I. Direct Blue 199, C.I. I. Acid Blue 249 or C.I. I. Reactive Blue 71 and the like of the phthalocyanine dye [for _{example, Cu-Pc- (SO 3 Na} ) m: a mixture of m = 1 to 4]

B: phthalocyanine-based dyes described in Patent Documents 1 to 3 and the like [for _{example, Cu-Pc- (SO 3 Na} ) m (SO 2 NH 2) n: a mixture of m + n = 1 to 4]

C: phthalocyanine-based coloring matter described in Patent Literature 4 and the like [for _{example, Cu-Pc- (CO 2 H} ) m (CONR 1 R 2) n: m + n = 0~4 number]

D: phthalocyanine-based coloring matter described in Patent Literature 5 and the like [for _{example, Cu-Pc- (SO 3 H} ) m (SO 2 NR 1 R 2) n: m + n = 0~4 number, and, m ≠ 0]

E: phthalocyanine-based coloring matter described in Patent Literature 6 and the like [for _{example, Cu-Pc- (SO 3 H} ) l (SO 2 NH 2) m (SO 2 NR 1 R 2) n: l + m + n = 0~4 number]

F: phthalocyanine-based coloring matter described in Patent Literature 7 and the like [for _{example, Cu-Pc- (SO 2 NR} 1 R 2) n: n = number of 1 to 5]

G: phthalocyanine dyes described in Patent Documents 8, 9, 10 and the like [phthalocyanine compounds in which the substitution position of the substituent is controlled, phthalocyanine dyes in which a substituent is introduced at the β-position]

H: Phthalocyanine dye having a pyridine ring described in Patent Document 11

I: Phthalocyanine dye having one triazine ring described in Patent Document 13, etc.

J: Phthalocyanine dye having two triazine rings described in Patent Document 14

Japanese Patent Laid-Open No. 62-190273 JP-A-7-138511 JP 2002-105349 A Japanese Patent Laid-Open No. 5-171085 Japanese Patent Laid-Open No. 10-140063 Japanese National Patent Publication No. 11-515048 JP 59-22967 JP 2000-303009 A Japanese Patent Laid-Open No. 2002-249677 JP 2004-315807 A JP 2003-34758 A JP 2002-80762 A WO2004087815 Japanese Patent Laid-Open No. 3-185080

C. currently widely used in general. I. Direct Blue 86 or C.I. I. A phthalocyanine dye represented by Direct Blue 199 has a feature that it is excellent in light resistance as compared with a generally known magenta dye or yellow dye.
On the other hand, phthalocyanine-based dyes have a greenish hue under acidic conditions, which is not preferable for cyan ink. Therefore, when these dyes are used as cyan ink, they are preferably used under neutral to alkaline conditions. However, even if the ink is neutral to alkaline, the hue of the printed matter may change greatly if the recording material used is acidic paper.

In addition, nitric oxide gas, ozone, and other oxidizing gases that are often taken up as environmental problems in recent years also change the color to green, and at the same time the print density decreases.

On the other hand, although the hue of triphenylmethane is good, it is very inferior to the phthalocyanine dye in light resistance, ozone resistance and moisture resistance.

In the future, if the field of use expands and is widely used for exhibitions such as advertisements, it is often exposed to light and active gases in the environment, so it has particularly good hue, light resistance and There is an increasing demand for pigments and inks that are excellent in resistance to active gases in the environment and are inexpensive. However, it is difficult to develop cyan dyes (for example, phthalocyanine dyes) and cyan inks that satisfy these requirements at a high level. So far, phthalocyanine dyes imparted with active gas resistance have been disclosed in Patent Documents 3, 8-14, etc., but satisfy all qualities such as hue, light resistance, ozone resistance, moisture resistance and bronze phenomenon. Cyan dye and cyan ink have not yet been obtained. Therefore, it has not yet fully satisfied the demands of the market.

An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a novel phthalocyanine dye having a good hue as a cyan ink, excellent in light resistance, ozone resistance and moisture resistance and greatly mitigating the bronze phenomenon, and further, the phthalocyanine An object of the present invention is to provide an ink suitable for ink jet recording using a dye and an ink jet recording method.

[式（１１１）中、Ｘ、ＹおよびＺ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アルコキシ基、置換もしくは無置換のシクロアルキルオキシ基、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ールアミノ基、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ジアルケニルアミノ基、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アリールチオ基、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。但し、Ｘ、Ｙ、Ｚの少なくとも１つは、スルホ基、カルボキシル基、またはイオン性親水性基を置換基として有する基である。]
（２）遊離酸として下記式（１）で表されるフタロシアニン化合物を含有する（１）に記載のインク

[式（１）中、Ｍは水素原子、金属原子、金属酸化物、金属水酸化物、または金属ハロゲン化物を表す。Ｒ₁、Ｒ₂は各々独立して、スルファモイル基、又は式（２）で表される置換スルファモイル基を表す。置換基はβ位に結合する。Ｘ、ＹおよびＺ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アルコキシ基、置換もしくは無置換のシクロアルキルオキシ基、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ールアミノ基、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ジアルケニルアミノ基、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アリールチオ基、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。但し、Ｘ、Ｙ、Ｚの少なくとも１つは、スルホ基、カルボキシル基、またはイオン性親水性基を置換基として有する基である。ａ、ｂ、ｃの和は３．０から４．０であり、ｂは０．３から２．０でありｃは０．１から１．０であり、残りはａである。]

（３）前記式（１）において、Ｘ、ＹおよびＺは、それぞれ独立して水酸基、スルホ基、カルボキシル基、アミノ基、モルホリノ基、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、ハロゲン原子からなる群から選択される置換基で置換されてもよい。）、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、アルコキシ基からなる群から選択される１種または２種以上の置換基で置換されてもよい。）、ベンジロキシ基（スルホ基で置換されてもよい。）、フェネチルオキシ基（スルホ基で置換されてもよい。）、アルキルアミノ基（スルホ基、カルボキシル基、水酸基、ウレイド基、アルコキシ基、ジアルキルアミノ基、アリールアミノ基、アリール基、ハロゲン原子、シアノ基からなる群から選択される置換基で置換されてもよい。）、アニリノ基（スルホ基、カルボキシル基、水酸基、ウレイド基、アルコキシ基、ジアルキルアミノ基、アリールアミノ基、アリール基、ハロゲン原子、シアノ基、アルキル基、ニトロ基、ヘテロ環基からなる群から選択される１種または２種以上の置換基で置換されてもよい。）、ナフチルアミノ基（スルホン酸基または水酸基で置換されてもよい）であり、Ｘ、Ｙ、Ｚの少なくとも１つは、スルホ基、カルボキシル基、またはイオン性親水性基を置換基として有する基である（１）から（２）のいずれか一項に記載のフタロシアニン化合物を含有するインク
（４）ＭがＣｕである（１）から（３）のいずれか一項に記載のフタロシアニン化合物を含有するインク
（５）有機溶剤を含有する（１）から（４）に記載のインク
（６）インクジェット記録用である（１）から（５）に記載のインク
（７）インク滴を記録信号に応じて吐出させて被記録材に記録を行うインクジェット記録方法において、インクとして（１）から（６）のいずれか一項に記載のインクまたはそのインクを含むインクセットを使用することを特徴とするインクジェット記録方法
（８）被記録材が情報伝達用シートである（７）に記載のインクジェット記録方法
（９）情報伝達用シートが表面処理されたシートであって、支持体上に白色無機顔料粒子を含有するインク受像層を有するシートである（８）に記載のインクジェット記録方法
（１０）（１）から（６）のいずれか一項に記載のインクまたはそのインクを含むインクセットを含有する容器
（１１）（１０）に記載の容器を有するインクジェットプリンタ
（１２）（１）から（６）のいずれか一項に記載のインクまたはそのインクを含むインクセットで着色された着色体
（１３）遊離酸として下記式（３）で表されるフタロシアニン色素

[式（３）中、ＭはＣｕを表す。Ｘ、ＹおよびＺは、水酸基、スルホ基、カルボキシル基、アミノ基、モルホリノ基、（Ｃ１〜Ｃ４）アルコキシ基（スルホ基、カルボキシル基、水酸基、ジ（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）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、ハロゲン原子からなる群から選択される置換基で置換されてもよい。）、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、アルコキシ基からなる群から選択される１種または２種以上の置換基で置換されてもよい。）、ベンジロキシ基（スルホ基で置換されてもよい。）、フェネチルオキシ基（スルホ基で置換されてもよい。）、モノ又はジ（Ｃ１〜Ｃ４）アルキルアミノ基（スルホ基、カルボキシル基、水酸基、ウレイド基、アルコキシ基、ジ（Ｃ１〜Ｃ４）アルキルアミノ基、アリールアミノ基、アリール基、ハロゲン原子、シアノ基からなる群から選択される置換基で置換されてもよい。）、アニリノ基（スルホ基、カルボキシル基、水酸基、ウレイド基、（Ｃ１〜Ｃ４）アルコキシ基、ジ（Ｃ１〜Ｃ４）アルキルアミノ基、アリールアミノ基、アリール基、ハロゲン原子、シアノ基、アルキル基、ニトロ基、ヘテロ環基からなる群から選択される１種または２種以上の置換基で置換されてもよい。）、ナフチルアミノ基（スルホン酸基または水酸基で置換されてもよい）であり、Ｘ、Ｙ、Ｚの少なくとも１つは、スルホ基、カルボキシル基、またはイオン性親水性基を置換基として有する基である。ａ、ｂ、ｃの和は３．０から４．０であり、ｂは０．３から２．０でありｃは０．１から１．０であり、残りはａである。]
（１４）Ｘ、ＹおよびＺは、それぞれ独立して、水酸基、スルホ基、カルボキシル基、アミノ基、モルホリノ基、モノ又はジ（Ｃ１〜Ｃ４）アルキルアミノ基（スルホ基、カルボキシル基、水酸基、ウレイド基、アルコキシ基、ジ（Ｃ１〜Ｃ４）アルキルアミノ基、アリールアミノ基、アリール基、ハロゲン原子、シアノ基からなる群から選択される置換基で置換されてもよい。）、アニリノ基（スルホ基、カルボキシル基、水酸基、ウレイド基、（Ｃ１〜Ｃ４）アルコキシ基、ジ（Ｃ１〜Ｃ４）アルキルアミノ基、アリールアミノ基、アリール基、ハロゲン原子、シアノ基、アルキル基、ニトロ基、ヘテロ環基からなる群から選択される１種または２種以上の置換基で置換されてもよい。）、ナフチルアミノ基（スルホン酸基または水酸基で置換されてもよい）で表される（１）から（３）に記載のフタロシアニン色素
（１５）Ｘがスルホ基又はカルボキシル基で置換されたアニリノ基、またはスルホ基で置換されたナフチルアミノ基であり、Ｙがスルホ基又はカルボキシル基で置換されたアニリノ基、またはスルホ基で置換されたナフチルアミノ基であり、Ｚがスルホ基又はカルボキシル基で置換されたアニリノ基、またはスルホ基で置換されたナフチルアミノ基、またはスルホ基またはカルボキシル基で置換された（Ｃ１〜Ｃ４）アルキルアミノ基、またはアミノ基、またはモルホリノ基、または水酸基である（１３）に記載のフタロシアニン色素
（１６）式（４）で表されるフタロシアニン化合物又はその塩に塩素化剤を反応させ、クロロスルホン基に変換した後、アミノ化剤の存在下、２，４−ジアミノベンゼンスルホン酸と反応させて、得られた色素混合物に式（５）と式（６）で表される化合物を順次反応させて得られる（１３）に記載のフタロシアニン色素の製造方法

［式（５）中、Ｍは水素原子、金属原子、金属酸化物、金属水酸化物、または金属ハロゲン化物を、Ｌはプロトン、アルカリ金属イオン、アルカリ土類金属イオン、金属イオン、有機アミンのオニウムイオンまたはアンモニウムイオンをそれぞれ表す。ｅ、ｆ、ｇ、ｈは０又は１であり、その和は３〜４の整数である。］

（１７）アミノ化剤がアンモニア水である（１６）に記載の製造方法
に関する。 The present inventors have examined in detail phthalocyanine dyes having good hue, light resistance, and ozone resistance, and found that the above problems can be solved by using a specific phthalocyanine dye as an ink dye. The headline and the present invention were completed. More specifically, the present invention relates to a phthalocyanine compound characterized by introducing a sterically hindered substituent having two triazine rings as a substituent. The colorant of the present invention has a good hue such as cyan, has excellent light resistance (durability to light), moisture resistance (durability under high humidity), ozone resistance (durability to ozone gas), and in bronze phenomenon Found that this was greatly relieved, and the present invention was completed.
That is, the present invention
(1) Ink containing a phthalocyanine compound having a group represented by the following formula (111) as a substituent at the β-position

[In the formula (111), X, Y and Z are each independently a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy 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 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 dialkenylamino group, substituted Or an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, or a substituted or unsubstituted alkenylthio group. However, at least one of X, Y, and Z is a group having a sulfo group, a carboxyl group, or an ionic hydrophilic group as a substituent. ]
(2) The ink according to (1), which contains a phthalocyanine compound represented by the following formula (1) as a free acid:

[In Formula (1), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide. R ₁ and R ₂ each independently represent a sulfamoyl group or a substituted sulfamoyl group represented by formula (2). The substituent is bonded to the β position. X, Y and Z are each independently a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a 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 diamino Alkenylamino group, substituted or unsubstituted al Thio 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. However, at least one of X, Y, and Z is a group having a sulfo group, a carboxyl group, or an ionic hydrophilic group as a substituent. The sum of a, b, and c is 3.0 to 4.0, b is 0.3 to 2.0, c is 0.1 to 1.0, and the rest is a. ]

(3) In the formula (1), X, Y and Z are each independently a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a morpholino group, an alkoxy group (a sulfo group, a carboxyl group, a hydroxyl group, a dialkylamino group, An arylamino group, an acetylamino group, an alkoxy group, an aryl group, a cyano group, or a halogen atom, which may be substituted with a substituent selected from the group consisting of an arylamino group, a phenoxy group (a sulfo group, a carboxyl group, a ureido group, an alkyl group). Group, may be substituted with one or more substituents selected from the group consisting of alkoxy groups), a benzyloxy group (which may be substituted with a sulfo group), a phenethyloxy group (with a sulfo group). May be substituted.), Alkylamino group (sulfo group, carboxyl group, hydroxyl group, ureido group, alkoxy group, dialkyl amine) Group, an arylamino group, an aryl group, a halogen atom, a cyano group, and an anilino group (sulfo group, carboxyl group, hydroxyl group, ureido group, alkoxy group, It may be substituted with one or more substituents selected from the group consisting of a dialkylamino group, an arylamino group, an aryl group, a halogen atom, a cyano group, an alkyl group, a nitro group, and a heterocyclic group. , A naphthylamino group (which may be substituted with a sulfonic acid group or a hydroxyl group), and at least one of X, Y, and Z is a group having a sulfo group, a carboxyl group, or an ionic hydrophilic group as a substituent. Any one of (1) to (3), wherein the ink (4) M containing Cu is a phthalocyanine compound according to any one of (1) to (2). Ink containing the phthalocyanine compound described in (5) Ink described in (1) to (4) containing an organic solvent (6) Ink described in (1) to (5) for ink jet recording (7) Ink In an ink jet recording method in which droplets are ejected in accordance with a recording signal and recording is performed on a recording material, the ink according to any one of (1) to (6) or an ink set including the ink is used as ink. (8) The ink-jet recording method according to (7), wherein the recording material is a sheet for information transmission. (9) The sheet for information transmission is a surface-treated sheet, on a support. The inkjet recording method (10) according to any one of (1) to (6), wherein the sheet has an ink image-receiving layer containing white inorganic pigment particles. An ink according to any one of (1) to (6), or an ink of the ink according to any one of the containers (11) and (10) containing the ink or an ink set containing the ink. Colored product colored with ink set containing (13) Phthalocyanine dye represented by the following formula (3) as a free acid

[In formula (3), M represents Cu. X, Y, and Z are a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a morpholino group, a (C1-C4) alkoxy group (a sulfo group, a carboxyl group, a hydroxyl group, a di (C1-C4) alkylamino group, (C1- C4) may be substituted with a substituent selected from the group consisting of arylamino group, acetylamino group, alkoxy group, aryl group, cyano group and halogen atom), phenoxy group (sulfo group, carboxyl group, ureido group) , May be substituted with one or more substituents selected from the group consisting of an alkyl group and an alkoxy group.), A benzyloxy group (which may be substituted with a sulfo group), a phenethyloxy group (sulfo). A mono- or di (C1-C4) alkylamino group (sulfo group, carboxyl group, hydroxyl group, ureido group, al A xy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, and a cyano group (which may be substituted with a substituent selected from the group consisting of cyano group), an anilino group (sulfo group, carboxyl group). Group consisting of a group, a hydroxyl group, a ureido group, a (C1-C4) alkoxy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, a cyano group, an alkyl group, a nitro group, and a heterocyclic group Or a naphthylamino group (which may be substituted with a sulfonic acid group or a hydroxyl group), and at least one of X, Y, and Z Is a group having a sulfo group, a carboxyl group, or an ionic hydrophilic group as a substituent. The sum of a, b, and c is 3.0 to 4.0, b is 0.3 to 2.0, c is 0.1 to 1.0, and the rest is a. ]
(14) X, Y and Z are each independently a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a morpholino group, a mono or di (C1-C4) alkylamino group (a sulfo group, a carboxyl group, a hydroxyl group, a ureido Group, an alkoxy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, and a cyano group (which may be substituted), an anilino group (sulfo group) , Carboxyl group, hydroxyl group, ureido group, (C1-C4) alkoxy group, di (C1-C4) alkylamino group, arylamino group, aryl group, halogen atom, cyano group, alkyl group, nitro group, heterocyclic group Or a naphthylamino group (a sulfonic acid group or a hydroxyl group). The phthalocyanine dye (15) X described in (1) to (3) represented by (which may be substituted) is an anilino group substituted with a sulfo group or a carboxyl group, or a naphthylamino group substituted with a sulfo group Y is an anilino group substituted with a sulfo group or a carboxyl group, or a naphthylamino group substituted with a sulfo group, and Z is substituted with an anilino group substituted with a sulfo group or a carboxyl group, or a sulfo group The phthalocyanine dye (16) according to the formula (4), which is a naphthylamino group, or a (C1-C4) alkylamino group substituted with a sulfo group or a carboxyl group, an amino group, a morpholino group, or a hydroxyl group A chlorinating agent is reacted with the phthalocyanine compound represented by Described in (13), which is obtained by reacting with a compound represented by formula (5) and formula (6) in order by reacting with 2,4-diaminobenzenesulfonic acid in the presence of an agent. For producing phthalocyanine dye

[In the formula (5), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide, and L represents a proton, an alkali metal ion, an alkaline earth metal ion, a metal ion, or an organic amine. Each represents an onium ion or an ammonium ion. e, f, g, and h are 0 or 1, and the sum is an integer of 3-4. ]

(17) The production method according to (16), wherein the aminating agent is aqueous ammonia.

The ink using the phthalocyanine coloring matter of the present invention has an excellent hue as a cyan ink and is excellent in light resistance, ozone resistance and moisture resistance. 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 ink using the phthalocyanine dye of the present invention is extremely useful as an ink for ink jet recording.

The present invention will be described in detail. The present invention is a phthalocyanine dye mixture having an unsubstituted sulfamoyl group and an ionic hydrophilic group in a phthalocyanine ring, and an ink using the same. Patent Document 3 discloses that a phthalocyanine dye mixture having an unsubstituted sulfamoyl group has good ozone resistance. However, the present inventor has found that the bronzing phenomenon is greatly alleviated by introducing a sterically hindered substituted sulfamoyl group having two triazine rings.

In general, phthalocyanine derivatives inevitably contain substitution position isomers of the substituent R _n (n = 1 to 16) in the formula (7) at the time of synthesis, but these substitution position isomers are distinguished from each other. Are often regarded as the same derivative. In this specification, for convenience, the positions on the benzene nucleus to which R _{1 to} R ₁₆ are bonded are defined as the 1st to 16th positions, respectively.

The phthalocyanine derivatives having different substitution positions are classified and defined as the following three types, and in the present specification, for convenience, when describing the phthalocyanine derivatives having different substitution positions, the following (1) β-position substitution type, (2) α -Position substitution type, (3) α, β-position mixed substitution type.

(1) β-position substitution type: Substituents at all or at least one of four positions selected from 2-position, 3-position, 6-position, 7-position, 10-position, 11-position, 14-position or 15-position The phthalocyanine compound which has.
(2) α-position substitution type: 1-position, 4-position, 5-position, 8-position, 9-position, 12-position, 13-position or 16-position, all or at least any one of four positions The phthalocyanine compound which has.
(3) α, β-position mixed substitution type: having at least two substituents at any position from the 1st position to the 16th position, at least one of the substituents being at the α-position and at least one at the same time A phthalocyanine compound having a substituent at the β-position.

In the formula (1), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide. Specific examples of metal atoms include, for example, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir , Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. Examples of the metal oxide include VO and GeO. Examples of the metal hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) ₂ , AlOH, and the like. Further, as the metal halide, for _{example, SiCl 2, VCl, VCl 2} , VOCl, FeCl, GaCl, ZrCl, AlCl , and the like. Among these, Cu, Ni, Zn, Al, and AlOH are preferable, and Cu is most preferable.

In the present specification, unless otherwise specified, the number of carbon atoms in the alkyl group, alkoxy group, alkenyl group, cycloalkyl group and the like is not particularly limited as long as the object of the present invention is achieved. In the following, the meanings of the terms “alkyl group”, “cycloalkyl group”, “aryl group”, “heterocyclic group”, “aralkyl group” and “alkenyl group” used in this specification will be shown. Unless otherwise specified, these represent the same meaning throughout the present specification, and for the sake of convenience, for example, when used as a substituent of an amino group or an oxy group such as a cycloalkylamino group or a heterocyclic oxy group. It shall have meaning.
Usually, the carbon number of the alkyl group, alkoxy group, alkenyl group, cycloalkyl group and the like is 1 to 16, preferably 1 to 12, more preferably 1 to 6, and further about 1 to 4.
However, about a cycloalkyl group, it is 3-12 normally, Preferably it is about 5-8.
Moreover, when these have a substituent, as long as the objective of this invention is achieved, the kind of 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 phosphoric acid group and the like. Derived group (such as phosphate ester group), hydroxyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group, halogen atom, cyano group, substituted or unsubstituted arylthio Groups and the like.
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.

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 phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

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, and 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). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

  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 phosphate 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. A group, a heterocyclic group, and a halogen atom. Of these, a sulfo group, a carboxyl group, a phosphate 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 heterocyclic rings may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group and halogen atom.

  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. (Please list specific examples of preferred aralkyl groups here). The aralkyl group may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), Examples thereof include a ureido group, an alkyl group, an alkoxy group, a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkenyl group include alkenyl groups having 1 to 12 carbon atoms. (Please list specific examples of preferred alkenyl groups here). Examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, and a cyano group. Can be mentioned. Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

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

Examples of the substituted or unsubstituted cycloalkyloxy group include cycloalkyloxy groups having 3 to 12 carbon atoms. Preferably, a C5-C8 cycloalkyloxy 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, and 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). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

Examples of the substituted or unsubstituted allyloxy group include a phenoxy group and a naphthyloxy group. Examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

  The heterocyclic ring in the above substituted or unsubstituted heterocyclic oxy group is preferably a 5-membered or 6-membered ring, which may be further condensed. Moreover, it may be an aromatic heterocycle or an aliphatic 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 heterocyclic rings may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group and halogen atom.

The number of carbon atoms of the alkoxy group in the alkoxy group (aralkyloxy group) substituted with the substituted or unsubstituted aryl group is about 1 to 12. Examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

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

Examples of the substituted or unsubstituted cycloalkylamino group include cycloalkylamino 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, and 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). Of these, a sulfo group, a carboxyl group, a phosphate 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 phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

  The heterocyclic ring in the substituted or unsubstituted heterocyclic amino group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Moreover, it may be an aromatic heterocycle or an aliphatic 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 heterocyclic rings may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group and halogen atom.

The alkylamino group (aralkyloamino group) substituted with the above substituted or unsubstituted aryl group has about 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate 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 phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

Examples of the substituted or unsubstituted dialkylamino group include a dialkylamino group having two alkyl groups having 1 to 12 carbon atoms as substituents. Examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

Examples of the substituted or unsubstituted dialkenylamino group include a dialkenylamino group having two alkenyl groups having 1 to 12 carbon atoms as substituents. Examples of the substitution include a group sulfo group, carboxyl group, phosphoric acid group, hydroxyl group, alkoxy group, amino group (which may be substituted with an alkyl group, aryl group and acetyl group) aryl group, halogen atom, cyano group, arylthio group (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate 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 phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

Examples of the substituted or unsubstituted cycloalkylthio group include cycloalkylthio groups having 3 to 12 carbon atoms. The cycloalkyl group in the cycloalkylthio group is preferably a cycloalkyl group having 5 to 8 carbon atoms. 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, and 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). Of these, a sulfo group, a carboxyl group, a phosphate 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 phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

  The heterocyclic ring in the above substituted or unsubstituted heterocyclic thio group is preferably a 5-membered or 6-membered ring, which 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 heterocyclic rings may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an amino group (substituted with an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group and halogen atom.

The alkylthio group in the alkylthio group (aralkylthio group) substituted with the substituted or unsubstituted aryl group has about 1 to 12 carbon atoms. Examples of the substituent include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, a halogen atom, a cyano group, and an arylthio group. (May be substituted with a sulfo group or the like). Of these, a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group are preferable.

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

Specific examples of combinations of M, X, Y, and Z in the phthalocyanine dye represented by the formula (1) of the present invention are shown in Tables 1 to 5. The phthalocyanine dye used in the present invention is limited to the following examples. Is not to be done. In the table, functional groups such as sulfonic acid are described in the form of free acid.

The phthalocyanine dye of the present invention is obtained by reacting phthalocyanine sulfonic acid chloride with ammonia and 2,4-diaminobenzene sulfonic acid to convert it to a substituted sulfamoyl group, and further by condensation with the above formulas (5) and (6). .
Phthalocyanine sulfonic acid chloride can be obtained by reacting (metal) phthalocyanine with chlorosulfonic acid, and 4-sulfophthalic acid derivatives, or 4-sulfophthalic acid derivative and (anhydrous) phthalic acid derivative are present in the presence of a metal compound. It can also be obtained by reacting a compound obtained by the reaction below with a chlorinating agent to convert a sulfo group into a chlorosulfone group.
In the former case, an α, β-position mixed substitution type phthalocyanine dye is obtained (ratio of α-position substitution type: β-position substitution type is approximately 50:50), and in the latter case, a β-position substitution type phthalocyanine dye is obtained. can get. 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. The 4-sulfophthalic acid derivative available as a commercial product used as a raw material for synthesis of the β-position substitution type dye usually contains the 3-sulfophthalic acid derivative as an impurity in an amount of about 15 to 25% by mass. For this reason, the α-position substitution product derived from this impurity is mixed in the target phthalocyanine dye. In order to further enhance the effect of the present invention, that is, in order to obtain an ink having particularly high ozone resistance, it is preferable to use a raw material having a low content of the 3-sulfophthalic acid derivative as an impurity.
Furthermore, when reacting ammonia with the phthalocyanine sulfonic acid chloride, a side reaction in which a part of the sulfonic acid chloride is hydrolyzed and converted into a sulfo group can be considered. In this case, the sulfo-substituted phthalocyanine dye may be partially mixed as a by-product in the target sulfamoyl-substituted phthalocyanine dye, but there is no particular problem in the present invention.

In the phthalocyanine dye represented by the formula (3) of the present invention, a β-substituted product is a main component, that is, at least 60% or more, preferably 70% or more, more preferably 80% or more.

For the number of substituents a, b and c of the phthalocyanine dye of the present invention, the sum of a, b and c is from 3.0 to 4.0, b is from 0.3 to 2.0 and c is from 0.1 1.0 and the rest is a. In each case, b is preferably 0.5 or more, and c is preferably 0.3 or more. On the other hand, when the ratio of a and b is large, the ozone resistance increases, but the bronze phenomenon tends to occur. Therefore, considering the ozone resistance, bronze characteristics, ease of production, etc., the ratio of 2,4-diaminobenzenesulfonic acid, formula (5) and formula (6) is adjusted appropriately, and a balanced ratio is selected. do it.
In the present invention, in the synthesis of the dye, it is considered that the sulfonic acid chloride of the dye is partially hydrolyzed to become a sulfo group as described above, but it is difficult to distinguish both from the analysis. Therefore, in this specification, for convenience, it is represented as an unsubstituted sulfamoyl group. Therefore, when a sulfo group is formed as a by-product, the number of substituents a is expressed as the total amount of unsubstituted sulfamoyl groups and sulfo groups.

Specific examples of more preferable combinations of M, X, Y, and Z in the phthalocyanine dye of the present invention are shown in Table 5. In the table, functional groups such as sulfonic acid are described in the form of free acid.

The manufacturing method of the pigment | dye of Formula (1) of this invention is demonstrated. In the present specification, for the sake of convenience, phthalic acid and / or phthalic anhydride is referred to as (anhydrous) phthalic acid. In addition, even when expressed as (anhydrous) phthalic acid derivatives, (anhydrous) phthalic acid has the same meaning.

First, a metal phthalocyanine sulfonic acid represented by the formula (4) is synthesized. As described above, the α-position substitution product derived from the raw material is by-produced in the phthalocyanine dye of the present invention, but in the description of the production method, it is described as the β-position substitution product of the main component.
In order to synthesize the formula (4), for example, it is obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (anhydrous) phthalic acid derivative in the presence of a catalyst and a metal compound.
It is possible to adjust the number of sulfo groups, that is, the number of e to h by changing the molar ratio of the reaction of 4-sulfophthalic acid and unsubstituted (anhydrous) phthalic acid. 4-sulfophthalic acid derivatives include 4-sulfophthalic acid, 4-sulfophthalic anhydride, 4-sulfophthalimide, 4-sulfophthalonitrile, 4 or 5-sulfo-2-cyanobenzamide and 5-sulfo-1,3-diimino Examples thereof include isoindoline or a salt thereof. Of these, 4-sulfophthalic acid or a salt thereof is usually preferred. However, in the case of phthalic acid, phthalic anhydride and phthalimide, addition of urea is essential. The amount of urea used is 5 to 100 times the amount of 1 mol of the 4-sulfophthalic acid derivative.

The reaction is usually performed in the presence of a solvent, and an organic solvent having a boiling point of usually 100 ° C. or higher, more preferably 130 ° C. or higher is used as the solvent. 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 mass of the 4-sulfophthalic 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 mole per mole of 4-sulfophthalic acid derivative.

As metal compounds, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu , Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and other halides, carboxylates, sulfates, nitrates, acetylacetonates, carbonyl compounds, complexes Etc. Examples thereof include copper chloride, copper bromide, nickel chloride, nickel acetate, cobalt chloride, cobalt acetate, and cobalt acetylacetonate. The amount of the metal compound used is 0.15 to 0.35 times the mol of 4-sulfophthalic acid derivative or a total of 1 mol of 4-sulfophthalic acid derivative and unsubstituted (anhydrous) 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, metal phthalocyanine tetrasulfonic acid or a salt thereof is obtained 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 copper phthalocyanine tetrasulfonic acid whose M is copper, or its salt is synthesize | combined by the method of patent document 8, and e, f, g, and h in the said Formula (4) are each represented by 1 For example, 4-sulfophthalic acid (1 mol), copper (II) chloride (0.3 mol), ammonium phosphomolybdate (0.003 mol), urea (6 mol), ammonium chloride (0. 5 mol) can be obtained by reacting at 180 ° C. and then at room temperature for 6 hours.

  By reacting the phthalocyanine sulfonic acid represented by the formula (4) or a salt thereof with a chlorinating agent in a solvent such as an organic solvent, sulfuric acid, fuming sulfuric acid or chlorosulfonic acid, the following formula (8) is obtained. Metal phthalocyanine sulfonic acid chloride obtained. The chlorinating agent is preferably used in excess relative to the sulfo group of phthalocyanine sulfonic acid or a salt thereof, and the molar ratio with respect to the sulfo group is about 1 to 10 times, preferably 1.5 times or more. 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. In addition, the phthalocyanine dye of the present invention may partially include a mixture of a by-product in which the phthalocyanine nucleus is chlorinated and a dye having a sulfo group that remains partially unreacted without being chlorinated. However, there is no particular problem even if these by-products are mixed.

〔式中、Ｍ、ｅ、ｆ、ｇ、ｈは前記と同じ意味を表す。〕

[Wherein, M, e, f, g, h represent the same meaning as described above. ]

  Next, the obtained phthalocyanine tetrasulfonic acid chloride and 2,4-diaminobenzenesulfonic acid or aminating agent are usually pH 8-12, usually 0-70 ° C. in an organic solvent, water solvent, water-organic solvent mixed system or the like. Usually, by reacting for 1 to 20 hours, a sulfamoyl metal phthalocyanine represented by the following formula (9) is obtained. Examples of the organic solvent used include, but are not limited to, acetonitrile, tetrahydrofuran, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine and the like. Examples of the aminating agent used in the reaction include, but are not limited to, ammonium salts such as ammonium chloride and ammonium sulfate, urea, aqueous ammonia, and ammonia gas.

〔式中、Ｍ、ａ、ｂ、ｃは前記と同じ意味を表す。〕

[Wherein M, a, b and c represent the same meaning as described above. ]

The amount of 2,4-diaminobenzenesulfonic acid used in the reaction is usually 1 mol or more of the theoretical value with respect to 1 mol of the phthalocyanine compound, but varies depending on the reaction conditions and is limited to these. It is not a thing.

Next, the amine, alcohol or thiol corresponding to X is usually 0.9 to 1.1 mol and 2,4,6-trichloro-S-triazine (cyanuric chloride) 1 mol in water, usually at a pH of 3 to 3. 7. Reaction is usually performed at 5 to 40 ° C. for 2 to 12 hours to obtain a condensate. Next, by reacting 0.5 to 1 mol of the phthalocyanine compound represented by the formula (9) usually at a pH of 4 to 10, usually 5 to 80 ° C., usually 0.5 to 20 hours, it is represented by the following formula (10). A phthalocyanine compound is obtained.

Further, the corresponding organic amine represented by the formula (6) is usually reacted with the compound of the formula (10) for 1 to 2 mol, usually pH 5 to 12, usually 20 to 80 ° C., usually 0.5 to 10 hours. As a result, the phthalocyanine compound of the present invention represented by the formula (3) is obtained. The order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.

The organic amine compound represented by the formula (6) can be synthesized as follows. That is, 0.9 to 1.1 mol of amines, alcohols or thiols corresponding to Y, and 1 mol of 2,4,6-trichloro-S-triazine (cyanuric chloride) in water usually have a pH of 3 to 3. 7. Reaction is usually performed at 5 to 40 ° C. for 2 to 12 hours to obtain a condensate. Next, a condensate is obtained by reacting 0.9 to 1.1 mol of amines, alcohols or thiols corresponding to Z, usually at pH 4 to 10, usually 5 to 80 ° C., usually 0.5 to 20 hours. . Furthermore, the compound represented by Formula (6) is obtained by making ethylenediamine react normally 10-30 mol, normally pH 5-12, normally 20-80 degreeC, and 0.5-10 hours normally. The order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.

In addition, the phthalocyanine dye of the present invention has a by-product in which a phthalocyanine dye (Pc) forms a dimer (for example, Pc-γ-Pc) or a trimer via a divalent linking group (γ). It is theoretically considered that it is generated and mixed in the target dye. In this case, examples of the divalent linking group represented by γ include a sulfonyl group (—SO ₂ —) and —SO ₂ —NH—SO ₂ —. However, there is no problem even if these are mixed.

The phthalocyanine dye of the present invention obtained as described above 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.
In general, the dye of the present invention is obtained in the form of a mixture of at least one compound represented by the formula (3), but there is no problem even if it is a mixture.

The cyan ink of the present invention contains the phthalocyanine dye of the above formula (3) produced by the above method and is prepared using water as a medium. When this ink is used as an ink for ink jet recording, the phthalocyanine dye is used. The content of anions such as Cl ^- and SO ₄ ^2- contained is preferably small, and the standard of the content is 5% by mass or less as the total content of Cl ^- and SO ₄ ^{2- in} the phthalocyanine dye, preferably Is 3% by mass or less, more preferably 1% by mass or less, and 1% by mass or less in the ink. Cl ^- and SO ₄ in the production of phthalocyanine dyes of ² less present invention, stirring the dried product or a wet cake of the phthalocyanine dye of the usual methods or the present invention using a reverse osmosis membrane for example an alcohol, and a mixed solvent of water Then, it may be desalted by filtration, drying or the like. 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 an ion chromatogram method.

When the cyan ink of the present invention is used as an ink for ink jet recording, an ink having a low content of heavy metals (ions) such as zinc and iron, metals such as calcium and silica (cations), etc. contained in the phthalocyanine dye is used. Are preferred (except for metals contained in the phthalocyanine skeleton (M in Formula (1) and Formula (3)). 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 the purified and dried phthalocyanine dye. The contents of heavy metal (ion) and metal (cation) are measured by an ion chromatogram method, an atomic absorption method or an ICP (Inductively Coupled Plasma) emission analysis method.

The phthalocyanine dye of the formula (1) is usually contained in the ink of the present invention in an amount of 0.1 to 8% by mass, preferably 0.3 to 6% by mass. The low-density ink usually contains 0.1 to 2.5% by mass of the phthalocyanine dye of the present invention.

If necessary, the ink of the present invention may further contain 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 of the present invention include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol, Carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydro Heterocyclic ketones such as pyrimido-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 glycol (C2 such as 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. To 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.

Preferred examples of the water-soluble organic solvent include mono- or polyhydric alcohols having 3 to 8 carbon atoms and 2-pyrrolidone optionally having an alkyl substituent having 1 to 3 carbon atoms. Those having 2 to 3 groups are preferred. 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 is there. 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, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. 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) 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 preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Examples of the ultraviolet absorber include a compound that emits fluorescence by absorbing ultraviolet rays represented by benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, or benzoxazole compounds, so-called fluorescence. Brighteners 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. Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol phosphate ester, alkyl phosphate ester, alkyl allyl sulfonate, diethyl sulfo Examples thereof include oxalate, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like. 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 octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate Esters such as ate, polyoxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7 Acetylene glycols such as diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, Surfhinol 104, 104PG50, 82 manufactured by Nissin Chemical) 465, Olfin STG, etc.). 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 highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, or silicone-based compound is used as necessary.

In producing the ink of the present invention, there is no particular limitation on the order in which the respective drugs are dissolved. In preparing the ink, the water to be used is preferably one having few impurities such as ion exchange water or distilled water. Furthermore, if necessary, fine filtration may be performed using a membrane filter to remove impurities. When used as ink for an inkjet printer, it is preferable to perform fine filtration. 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 of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full-color image, 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, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); Azomethine dyes having open-chain active methylene compounds, etc .; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, etc. Examples thereof include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

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 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, for example, yellow, magenta, and cyan colors only when a part of the chromophore is dissociated on paper when inkjet printing is performed. Further, it may be an inorganic cation such as ammonium, an organic cation such as pyridinium or a quaternary ammonium salt, or a polymer cation having them in a partial structure.

Examples of applicable black pigments include disazo, trisazo, and tetraazo dyes, and carbon black dispersions.

The ink of the present invention can be used in recording methods such as printing, copying, marking, writing, drafting, 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 colored product of the present invention is a product colored with the phthalocyanine dye of the present invention, a mixture thereof, or an aqueous ink containing the same. 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 the pigment in the ink such as porous silica, alumina sol, and special ceramics are impregnated or coated with the cationic polymer on the base material, for example, polyvinyl alcohol or polyvinyl pyrrolidone. 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 called ink jet dedicated paper (film), glossy paper (film) and the like. Among these, it is said that ozone gas and other gases having an oxidizing action in the air are 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 Canon Inc.), Photographic Paper Crispier <High Gloss>, Photographic Paper <Glossy>, Photo Matte Paper (both made by Seiko Epson Corporation), Advanced Photo Paper (Glossy) Premium Glossy Film, Photo Paper (all Also from Hewlett-Packard Japan), Photo-like QP (manufactured by Konica Corporation), Takashi Place coated paper, photo glossy paper (both Sony Co., Ltd.), and the like. 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 the ink jet 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 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 of the present invention has a clear cyan color. In addition, it is possible to obtain a recorded matter that is particularly excellent in ozone resistance and excellent in light resistance and water resistance. By using it as a set of dark and light cyan inks, it is possible to obtain a recorded matter further excellent in ozone resistance, light resistance and water resistance. In addition, when used with other yellow, magenta, and other inks such as green, red, orange, and blue as necessary, color tone in a wide visible range can be developed, 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 specifically by way of examples. In the text, “parts” and “%” are based on mass unless otherwise specified.
The number of substituents of phthalocyanine was analyzed as follows, and the numerical value was calculated.
For the copper content, 0.1 g of a sample was precisely weighed, diluted with Millipore water, and then analyzed by ICP emission spectrometry. Water was analyzed by Karl Fischer method using ethylene glycol as the solvent. For the inorganic content, 0.1 g of a sample was precisely weighed, dissolved in Millipore water, fixed to 100 ml, and then quantified by ion chromatography.
The organic content in the sample was calculated from the determined copper content, inorganic content, and moisture, and the average molecular weight in copper phthalocyanine was calculated by observing the ratio with the copper content. The number of substituents was calculated from the difference between the calculated average molecular weight and the molecular weight of the copper phthalocyanine used. Moreover, what oxidatively decomposed copper phthalocyanine with an oxidizing agent such as hydrogen peroxide was measured by ¹ H-NMR, and the ratio of β-position substitution type was measured by calculating the proton ratio.

Example 1
(1) In a four-necked flask, 49.2 parts of 4-sulfophthalic acid (manufactured by Pilot Corporation, 50% aqueous solution, containing 20% 3-sulfophthalic acid) was added and stirred, and 17.7 parts of 25% aqueous sodium hydroxide solution was added. 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 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 (11) Of copper phthalocyanine tetrasulfonic acid tetrasodium salt (19.1 parts) was obtained as blue crystals. λmax: 629 nm (in aqueous solution).

(2) Synthesis of (copper phthalocyanine tetrasulfonic acid chloride (β-position substituted type) (in the formula (8), M is Cu, and e, f, g and h are all 1) ))
While stirring, 784 parts of chlorosulfonic acid was gradually charged with 9.84 parts of copper sodium phthalocyanine tetrasulfonate at 60 ° C. or lower, and reacted at 120 ° C. for 4 hours. Next, the reaction solution was cooled to 70 ° C., 35.7 parts of thionyl chloride was added dropwise over 30 minutes, and the reaction was performed at 70 ° C. for 3 hours. The reaction solution was cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, the precipitated crystals were filtered, washed with 100 parts of ice-cooled 2% aqueous hydrochloric acid, and a wet cake of copper phthalocyanine tetrasulfonic acid chloride 41. 6 parts were obtained.

（２）（ウエットケーキと２，４−ジアミノベンゼンスルホン酸との縮合）
氷水５０部中に（１）で得られた銅フタロシアニンテトラスルホン酸クロリドのウェットケーキ４１．６部を加え、５℃以下で撹拌懸濁した。１０分後、１０℃以下を保持しながら、２，４−ジアミノベンゼンスルホン酸を１４．１部を投入し、２８％アンモニア水を添加しながら、ｐＨ８．０を保持した。同ｐＨを保持したまま、１時間かけて２０℃まで昇温し、同温度で８時間保持した。この時の液量は１２５部であった。反応液を５０℃に昇温し、塩化ナトリウム１２．５部（対液１０％）を加え３０分撹拌した後、２０分かけて塩酸にてｐＨ１．０に調節した後、濾過、２０％塩化ナトリウム水溶液１００部で洗浄し、遊離酸として下記式（１３）で表される化合物のウェットケーキ７９．３部を得た。この化合物を乾燥し、銅分、無機分を定量し、平均分子量を算出したところ９９９．１であった。この結果から式（１３）におけるｂとｃの総和は０．６９であると算出した。

(2) (Condensation of wet cake with 2,4-diaminobenzenesulfonic acid)
41.6 parts of the copper phthalocyanine tetrasulfonic acid chloride wet cake obtained in (1) was added to 50 parts of ice water and suspended by stirring at 5 ° C. or lower. Ten minutes later, 14.1 parts of 2,4-diaminobenzenesulfonic acid was added while maintaining the temperature at 10 ° C. or lower, and pH 8.0 was maintained while adding 28% aqueous ammonia. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour, and kept at the same temperature for 8 hours. The liquid volume at this time was 125 parts. The temperature of the reaction solution was raised to 50 ° C., 12.5 parts of sodium chloride (10% to the solution) was added and stirred for 30 minutes, then adjusted to pH 1.0 with hydrochloric acid over 20 minutes, filtered, and 20% chloride. This was washed with 100 parts of an aqueous sodium solution to obtain 79.3 parts of a wet cake of a compound represented by the following formula (13) as a free acid. This compound was dried, the copper content and the inorganic content were quantified, and the average molecular weight was calculated to be 999.1. From this result, the sum of b and c in the equation (13) was calculated to be 0.69.

（３）｛下記式（１４）（式（６）において、Ｙ：アニリン−２，５−ジスルホン酸、Ｚ：モルホリノである化合物）の合成｝
氷水３００部中にリパールＯＨ（商品名、アニオン界面活性剤、ライオン株式会社製）１．１部、塩化シアヌル３６．８部を投入し３０分間攪拌した。次にアニリン−２，５−ジスルホン酸モノナトリウム塩５８．０部を投入し、２５％水酸化ナトリウム水溶液を添加しながらｐＨ２．７〜３．０を保持し、１０〜１５℃で２時間、２５〜３０℃で１時間反応を行った。次に反応液を１０℃以下に冷却した後、この反応液にモルホリン１７．６部を添加し、２５％水酸化ナトリウム水溶液を添加しｐＨ６．５〜７．０に調節した、１０〜１５℃で０．５時間反応、２７〜３０℃で１時間反応した。次に反応液に氷を添加し５℃以下に調整した。この反応液にエチレンジアミン１２０部を投入し、２０〜３０℃で３時間反応を行った。液量を７５０部に調整し、塩化ナトリウムを１５０部を投入し結晶を析出させた。析出した結晶をろ過分取し、２０％塩化ナトリウム水溶液２５０部で洗浄し、ウエットケーキ８５．１部を得た。得られたウエットケーキ８５．１部をメタノール２００部中に投入し、水２０部を加え６０℃で１時間懸濁攪拌させた後、ろ過、メタノールで洗浄、乾燥し、式（１４）で表される化合物の白色粉末５２．３部を得た。

(3) {Synthesis of the following formula (14) (in the formula (6), Y: a compound that is aniline-2,5-disulfonic acid, Z: morpholino)}
In 300 parts of ice water, 1.1 parts of Lipar OH (trade name, anionic surfactant, manufactured by Lion Corporation) and 36.8 parts of cyanuric chloride were added 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 liquid to 10 ° C. or lower, 17.6 parts of morpholine was added to the reaction liquid, and 25% aqueous sodium hydroxide solution was added to adjust the pH to 6.5 to 7.0. For 0.5 hour and at 27-30 ° C. for 1 hour. Next, ice was added to the reaction solution to adjust to 5 ° C. or lower. 120 parts of ethylenediamine was added to this reaction solution, and the reaction was performed at 20 to 30 ° 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 85.1 parts of a wet cake. 85.1 parts of the obtained wet cake was put into 200 parts of methanol, 20 parts of water was added, and suspended and stirred at 60 ° C. for 1 hour, followed by filtration, washing with methanol, and drying. 52.3 parts of a white powder of the compound to be obtained were obtained.

（４）｛下記式（１５）（式（３）において、Ｍ：Ｃｕ、Ｘ：アニリン−２，５−ジスルホン酸、Ｙ：アニリン−２，５−ジスルホン酸、Ｚ：モルホリノである化合物）の合成｝
氷水３０部中にリパールＯＨ（商品名、アニオン界面活性剤、ライオン株式会社製）０．０３部、塩化シアヌル３．６４部を投入し３０分間攪拌した。次にアニリン‐２，５‐ジスルホン酸モノナトリウム塩５．８部を投入し、２５％水酸化ナトリウム水溶液を添加しながらｐＨ２．７〜３．０を保持し、１０〜１５℃で２時間、２５〜３０℃で１時間反応を行った。次に、水２００部中に上記式（１３）の化合物のウエットケーキ７９．３部を添加し、２５％水酸化ナトリウム水溶液を添加しｐＨ９．０〜１０．０、温度４５〜５０℃に調節した溶液に、この反応液を添加し、ｐＨ８．５〜９．０、４０〜４５℃で５時間反応した。次に反応液に式（１４）の化合物１０．４部を投入し、ｐＨ９．５〜１０．０、２０〜３０℃で３時間反応を行った。液量を６００部に調整し、塩化ナトリウムを１２０部を投入し、その後濃塩酸にてｐＨ０．７〜０．８に調節し結晶を析出させた。析出した結晶をろ過分取し、２０％塩化ナトリウム水溶液１００部で洗浄し、ウエットケーキ６４．１部を得た。得られたウエットケーキ６４．１部をメタノール３１０部中に投入し、水３１部を加え６０℃で１時間懸濁攪拌させた後、ろ過、メタノールで洗浄、乾燥し、青色粉末として式（１８）の化合物の混合物１０．４部を得た。この化合物を乾燥し、銅分、無機分を定量し、平均分子量を算出したところ１１５９．５であった。この結果から式（１５）におけるｂは０．４８、ｃは０．２１であると算出した。水中でのλmaxは６１２．０ｎｍであった

(4) {In the following formula (15) (in the formula (3), M: Cu, X: aniline-2,5-disulfonic acid, Y: aniline-2,5-disulfonic acid, Z: morpholino) Composition}
In 30 parts of ice water, 0.03 part of Lipar OH (trade name, anionic surfactant, manufactured by Lion Corporation) and 3.64 parts of cyanuric chloride were added and stirred for 30 minutes. Next, 5.8 parts of aniline-2,5-disulfonic acid monosodium salt was added, the pH was maintained at 2.7 to 3.0 while adding 25% aqueous sodium hydroxide, and the mixture was maintained at 10 to 15 ° C. for 2 hours. Reaction was performed at 25-30 degreeC for 1 hour. Next, 79.3 parts of a wet cake of the compound of the above formula (13) is added to 200 parts of water, and a 25% aqueous sodium hydroxide solution is added to adjust the pH to 9.0 to 10.0 and the temperature to 45 to 50 ° C. This reaction solution was added to the solution, and reacted at pH 8.5 to 9.0 and 40 to 45 ° C. for 5 hours. Next, 10.4 parts of the compound of formula (14) was added to the reaction solution, and reacted at pH 9.5 to 10.0, 20 to 30 ° C. for 3 hours. The liquid volume was adjusted to 600 parts, 120 parts of sodium chloride was added, and then the pH was adjusted to 0.7 to 0.8 with concentrated hydrochloric acid to precipitate crystals. The precipitated crystals were collected by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 64.1 parts of a wet cake. 64.1 parts of the obtained wet cake was put into 310 parts of methanol, 31 parts of water was added and suspended and stirred at 60 ° C. for 1 hour, followed by filtration, washing with methanol, and drying to obtain the formula (18 ) Was obtained 10.4 parts of a mixture of compounds. This compound was dried, the copper content and the inorganic content were quantified, and the average molecular weight was calculated to be 1159.5. From this result, b in formula (15) was calculated to be 0.48 and c was 0.21. Λmax in water was 612.0 nm

Example 2
(1) {Synthesis of the following formula (16) (in the formula (6), Y: aniline-2,5-disulfonic acid, Z: amino compound)}
In 300 parts of ice water, 1.1 parts of Lipar OH (trade name, anionic surfactant, manufactured by Lion Corporation) and 36.8 parts of cyanuric chloride were added 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 10 ° C. or less, 18.2 parts of 28% aqueous ammonia was added to the reaction solution. While adding a 25% aqueous sodium hydroxide solution, the pH was maintained at 9.0 to 10.0, and the reaction was performed at 10 to 15 ° C for 0.5 hours and at 27 to 30 ° C for 1 hour. Next, ice was added to the reaction solution to adjust to 5 ° C. or lower. 120 parts of ethylenediamine was added to this reaction solution, and the reaction was performed at 20 to 30 ° 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 92.1 parts of a wet cake. 92.1 parts of the obtained wet cake was put into 200 parts of methanol, 20 parts of water was added and suspended and stirred at 60 ° C. for 1 hour, followed by filtration, washing with methanol, and drying. 55.3 parts of a white powder of the compound obtained are obtained.

（２）｛下記式（１７）（式（３）において、Ｍ：Ｃｕ、Ｘ：アニリン−２，５−ジスルホン酸、Ｙ：アニリン−２，５−ジスルホン酸、Ｚ：アミノである化合物）の合成｝
氷水３０部中にリパールＯＨ（商品名、アニオン界面活性剤、ライオン株式会社製）０．１部、塩化シアヌル３．６４部を投入し３０分間攪拌した。次にアニリン−２，５−ジスルホン酸モノナトリウム塩５．８部を投入し、２５％水酸化ナトリウム水溶液を添加しながらｐＨ２．７〜３．０を保持し、１０〜１５℃で２時間、２５〜３０℃で１時間反応を行った。次に、水２００部中に上記式（１３）の化合物のウエットケーキ７９．３部を添加し、２５％水酸化ナトリウム水溶液を添加しｐＨ９．０〜１０．０、温度４５〜５０℃に調節した溶液に、この反応液を添加し、ｐＨ８．５〜９．０、４０〜４５℃で５時間反応した。次に反応液に式（１６）の化合物８．９部を投入し、ｐＨ９．５〜１０．０、２０〜３０℃で３時間反応を行った。液量を６５０部に調整し、塩化ナトリウムを１３０部を投入し、その後濃塩酸にてｐＨ０．７〜０．８に調節し結晶を析出させた。析出した結晶をろ過分取し、２０％塩化ナトリウム水溶液２００部で洗浄し、ウエットケーキ６１．４部を得た。得られたウエットケーキ６１．４部をメタノール３００部中に投入し、水３０部を加え６０℃で１時間懸濁攪拌させた後、ろ過、メタノールで洗浄、乾燥し、青色粉末として式（１７）の化合物の混合物１０．４部を得た。この化合物の銅分、無機分を定量し、平均分子量を算出したところ１１１９．３であった。この結果から式（１５）におけるｂは０．４８、ｃは０．２１であると算出した。水中でのλmaxは６１１．０ｎｍであった

(2) {in the following formula (17) (in the formula (3), M: Cu, X: aniline-2,5-disulfonic acid, Y: aniline-2,5-disulfonic acid, Z: amino compound) Composition}
In 30 parts of ice water, 0.1 part of Lipar OH (trade name, anionic surfactant, manufactured by Lion Corporation) and 3.64 parts of cyanuric chloride were added and stirred for 30 minutes. Next, 5.8 parts of aniline-2,5-disulfonic acid monosodium salt was added, the pH was maintained at 2.7 to 3.0 while adding 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, 79.3 parts of a wet cake of the compound of the above formula (13) is added to 200 parts of water, and a 25% aqueous sodium hydroxide solution is added to adjust the pH to 9.0 to 10.0 and the temperature to 45 to 50 ° C. This reaction solution was added to the solution, and reacted at pH 8.5 to 9.0 and 40 to 45 ° C. for 5 hours. Next, 8.9 parts of the compound of formula (16) was added to the reaction solution, and reacted at pH 9.5 to 10.0, 20 to 30 ° C. for 3 hours. The liquid volume was adjusted to 650 parts, 130 parts of sodium chloride was added, and then the pH was adjusted to 0.7 to 0.8 with concentrated hydrochloric acid to precipitate crystals. The precipitated crystals were collected by filtration and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain 61.4 parts of a wet cake. 61.4 parts of the obtained wet cake was put into 300 parts of methanol, 30 parts of water was added and suspended and stirred at 60 ° C. for 1 hour, and then filtered, washed with methanol, and dried to obtain a formula (17 ) Was obtained 10.4 parts of a mixture of compounds. The copper content and inorganic content of this compound were quantified and the average molecular weight was calculated to be 1119.3. From this result, b in formula (15) was calculated to be 0.48 and c was 0.21. Λmax in water was 611.0 nm

Example 3 (Ink evaluation)
(A) Preparation of Ink Each component described in Table 7 below was mixed and dissolved, and filtered through a 0.45 μm membrane filter (manufactured by Advantech) to obtain an ink. The water used was ion exchange water. Further, the pH of the ink was adjusted with caustic soda to be pH = 9 to 10, and water was added so that the total amount became 100 parts. The ink was C-1 for the ink using the phthalocyanine dye obtained in Example 1 and C-2 for the ink using the phthalocyanine dye obtained in Example 2.

Table 7
Each phthalocyanine dye obtained in Examples 1-2 above 5.0 parts water + caustic soda 39.7 parts glycerin 15.0 parts urea 15.0 parts N-methyl-2-pyrrolidone 12.0 parts IPA (isopropyl alcohol) 8.0 parts butyl carbitol 5.0 parts Surfinol 104PG50 (manufactured by Nissin Chemical) 0.3 parts total 100.0 parts

As a comparative example, a dye for inkjet recording used as Direct Blue 199, a product name: Projet Cyan 1 (manufactured by Avecia: Comparative Example 1), and a phthalocyanine dye described in Synthesis Example 1 of Patent Document 8 (Comparative Example 2) In the following formula (102), M is a pigment of Cu), and in Table 4, No. 4 of the above-mentioned Patent Document 13. The same as the ink of Example 1 in Table 7, using the phthalocyanine dye described in Item 21 (Comparative Example 3, a dye in which M is Cu in the following formula (103) and a + b / c = 3.52 / 0.48) An ink was prepared with the composition. The ink using the product of Comparative Example 1 was C-A, the ink using the compound of Comparative Example 2 was C-B, and the ink using the compound of Comparative Example 3 was C-C.

(B) Inkjet printing Using an inkjet printer (product name: PIXUS ip4100 manufactured by Canon Inc.), exclusive paper A (Advanced Photo Paper (Glossy) Q7871A manufactured by Hewlett-Packard Japan), exclusive paper B (Seiko Epson Photographic Paper <Glossy) > KA420PSK) was subjected to ink jet recording.
At the time of printing, an image pattern was formed so that six gradations of reflection densities of 100%, 85%, 70%, 55%, 40%, and 25% 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.

(C) Evaluation of recorded image Hue evaluation The hue of the recorded image is measured using the colorimetric system (SpectroEye: GretagMacbeth) and the a ^* and b ^* values when the L ^{* of} the printed material is in the range of 40 to 80 are measured. did. The 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 a ^* and b ^* value exist in a preferred region. ×: Both a ^* and b ^* values exist outside a preferred region.

2. The test piece of the light fastness test recorded image was irradiated with a xenon weather meter (Model Ci4000 manufactured by ATLAS) at 0.36 W / m2 illuminance for 100 hours under the conditions of a bath temperature of 24 ° C. and a humidity of 60% RH. After the test, the reflection density before and after the test 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 three stages.
○: Residual rate 70% or more Δ: Residual rate 50 or more, less than 70% ×: Residual rate less than 50%

3. The test piece of the ozone resistance test record image was left for 8 hours at an ozone concentration of 12 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 before and after the test 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 three stages.
○: Residual rate 85% or more Δ: Residual rate 70 or more, less than 85 ×: Residual rate less than 70%

4). The specimen of the moisture resistance test recorded image was left for 7 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

5). Bronze evaluation Bronze evaluation is based on which level of bronzing occurs with respect to six levels of print density: 100%, 85%, 70%, 55%, 40%, and 25% density. Was visually evaluated. For the case where bronzing did not occur, OK, and for the case where bronzing occurred, the minimum density in the above six steps among the printing densities where bronzing occurred was described.

Table 8 (special paper A) shows the hue evaluation, the light resistance test result, the ozone resistance test result, and the moisture resistance test result of the recorded images obtained with the inks of C-1 to C-2, CA, and CB. ) And Table 9 (special paper B).

Table 8
Ink evaluation result: Exclusive paper A
Ink number Hue Light resistance Ozone resistance Moisture resistance Bronze resistance C-1 ○ ○ ○ ○ OK
C-2 ○ ○ ○ ○ OK
C-A △ ○ × ○ OK
CB ○ ○ × ○ OK
C-C ○ ○ ○ ○ 85%

Table 9
Ink evaluation result: Exclusive paper B
Ink number Hue Light resistance Ozone resistance Moisture resistance Bronze resistance C-1 ○ ○ ○ ○ 85%
C-2 ○ ○ ○ ○ OK
C-A ○ ○ × ○ OK
CB ○ ○ × ○ OK
C-C ○ ○ △ ○ 70%

As is apparent from Tables 8 and 9, the recorded images of the inks of Comparative Examples 1 and 2 represented by the ink numbers C-A and C-B have extremely high ozone resistance regardless of which special paper is used. It turned out to be inferior. Further, it can be seen that the recorded image of the ink of Comparative Example 3 represented by C-C has a problem in bronze property in any special paper and in ozone resistance in the special paper B. Compared with this, cyan inks C-1 and C-2 using the phthalocyanine dye of the present invention are extremely excellent in ozone resistance, and the bronze property is 85% concentration when C-1 is used in special paper B. Although a slight bronze phenomenon occurs, it has been proved that the special paper A does not cause a bronze phenomenon, and that there is no problem in hue, light resistance, and moisture resistance.

The ink using the phthalocyanine coloring matter of the present invention has an excellent hue as a cyan ink and is excellent in light resistance, ozone resistance and moisture resistance. 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 ink using the phthalocyanine dye of the present invention is extremely useful as an ink for ink jet recording.

Claims (16)

Ink containing a phthalocyanine dye represented by the following formula (3) as a free acid

[In formula (3), M represents Cu. X, Y, and Z are a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a morpholino group, a (C1-C4) alkoxy group (a sulfo group, a carboxyl group, a hydroxyl group, a di (C1-C4) alkylamino group, (C1- C4) may be substituted with a substituent selected from the group consisting of arylamino group, acetylamino group, alkoxy group, aryl group, cyano group and halogen atom), phenoxy group (sulfo group, carboxyl group, ureido group) , May be substituted with one or more substituents selected from the group consisting of an alkyl group and an alkoxy group.), A benzyloxy group (which may be substituted with a sulfo group), a phenethyloxy group (sulfo). A mono- or di (C1-C4) alkylamino group (sulfo group, carboxyl group, hydroxyl group, ureido group, al A xy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, and a cyano group (which may be substituted with a substituent selected from the group consisting of cyano group), an anilino group (sulfo group, carboxyl group). Group consisting of a group, a hydroxyl group, a ureido group, a (C1-C4) alkoxy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, a cyano group, an alkyl group, a nitro group, and a heterocyclic group Or a naphthylamino group (which may be substituted with a sulfonic acid group or a hydroxyl group), and at least one of X, Y, and Z Is a group having a sulfo group as a substituent. The sum of a, b, and c is 3.0 to 4.0, b is 0.3 to 2.0, c is 0.1 to 1.0, and the rest is a. ] X, Y and Z in the phthalocyanine dye represented by the formula (3) are each independently a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a morpholino group, a mono- or di (C1-C4) alkylamino group (sulfo A substituent selected from the group consisting of a group, a carboxyl group, a hydroxyl group, a ureido group, an alkoxy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, and a cyano group. .), Anilino group (sulfo group, carboxyl group, hydroxyl group, ureido group, (C1-C4) alkoxy group, di (C1-C4) alkylamino group, arylamino group, aryl group, halogen atom, cyano group, alkyl group , A nitro group, or a heterocyclic group, which may be substituted with one or more substituents selected from the group consisting of heterocyclic groups), naphthi The ink of claim 1 which is represented by an amino group (optionally substituted with a sulfonic acid group or a hydroxyl group) In the phthalocyanine dye represented by the formula (3), X is an anilino group substituted with a sulfo group or a carboxyl group, or a naphthylamino group substituted with a sulfo group, and Y is an anilino substituted with a sulfo group or a carboxyl group Or a naphthylamino group substituted with a sulfo group, and Z is substituted with an anilino group substituted with a sulfo group or a carboxyl group, or a naphthylamino group substituted with a sulfo group, or a sulfo group or a carboxyl group The ink according to claim 1, which is a (C1-C4) alkylamino group, an amino group, a morpholino group, or a hydroxyl group. The ink according to claims 1 to 3 containing an organic solvent The ink according to claims 1, which is for inkjet recording to 4 The ink according to any one of claims 1 to 5 or an ink set including the ink is used as an ink in an ink jet recording method in which ink droplets are ejected according to a recording signal to perform recording on a recording material. Ink jet recording method The inkjet recording method according to claim 6 , wherein the recording material is an information transmission sheet. 8. The inkjet recording method according to claim 7 , wherein the information transmission sheet is a surface-treated sheet having an ink image-receiving layer containing white inorganic pigment particles on a support. A container containing the ink according to any one of claims 1 to 5 or an ink set containing the ink. An ink jet printer having the container according to claim 9. Ink or has been colored article colored with the ink set including the ink claimed in any one of 5 Phthalocyanine dye represented by the following formula (3) as a free acid

[In formula (3), M represents Cu. X, Y, and Z are a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a morpholino group, a (C1-C4) alkoxy group (a sulfo group, a carboxyl group, a hydroxyl group, a di (C1-C4) alkylamino group, (C1- C4) may be substituted with a substituent selected from the group consisting of arylamino group, acetylamino group, alkoxy group, aryl group, cyano group and halogen atom), phenoxy group (sulfo group, carboxyl group, ureido group) , May be substituted with one or more substituents selected from the group consisting of an alkyl group and an alkoxy group.), A benzyloxy group (which may be substituted with a sulfo group), a phenethyloxy group (sulfo). A mono- or di (C1-C4) alkylamino group (sulfo group, carboxyl group, hydroxyl group, ureido group, al A xy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, and a cyano group (which may be substituted with a substituent selected from the group consisting of cyano group), an anilino group (sulfo group, carboxyl group). Group consisting of a group, a hydroxyl group, a ureido group, a (C1-C4) alkoxy group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, a cyano group, an alkyl group, a nitro group, and a heterocyclic group Or a naphthylamino group (which may be substituted with a sulfonic acid group or a hydroxyl group), and at least one of X, Y, and Z Is a group having a sulfo group as a substituent. The sum of a, b, and c is 3.0 to 4.0, b is 0.3 to 2.0, c is 0.1 to 1.0, and the rest is a. ] X, Y and Z are each independently a hydroxyl group, a sulfo group, a carboxyl group, an amino group, a morpholino group, a mono- or di (C1-C4) alkylamino group (a sulfo group, a carboxyl group, a hydroxyl group, a ureido group, an alkoxy group) Group, a di (C1-C4) alkylamino group, an arylamino group, an aryl group, a halogen atom, and a cyano group (which may be substituted with a substituent selected from the group consisting of cyano group), an anilino group (sulfo group, carboxyl group) , Hydroxyl group, ureido group, (C1-C4) alkoxy group, di (C1-C4) alkylamino group, arylamino group, aryl group, halogen atom, cyano group, alkyl group, nitro group, heterocyclic group May be substituted with one or more selected substituents), a naphthylamino group (substituted with a sulfonic acid group or a hydroxyl group). Phthalocyanine dye represented by the formula (3) according to claim 1 2 represented by may also) be X is an anilino group substituted with a sulfo group or a carboxyl group, or a naphthylamino group substituted with a sulfo group, and Y is an anilino group substituted with a sulfo group or a carboxyl group, or a naphthylamino substituted with a sulfo group An anilino group substituted with a sulfo group or a carboxyl group, a naphthylamino group substituted with a sulfo group, or a (C1-C4) alkylamino group substituted with a sulfo group or a carboxyl group, or amino group or a morpholino group, or a phthalocyanine dye represented by the formula (3) according to claim 1 2 is a hydroxyl group, Obtained by reacting the phthalocyanine compound represented by formula (4) or a salt thereof with a chlorinating agent to convert it to a chlorosulfone group, and then reacting with 2,4-diaminobenzenesulfonic acid in the presence of an aminating agent. the method of manufacturing a phthalocyanine dye represented by the formula (3) according to claim 1 2 obtained the compound represented by the obtained dye mixture to formula (5) and (6) by sequentially reacting

[In the formula ( 4 ), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide, L represents a proton, an alkali metal ion, an alkaline earth metal ion, a metal ion, or an organic amine. Each represents an onium ion or an ammonium ion. e, f, g, and h are 0 or 1, and the sum is an integer of 3-4. ]

[In the formula (5), X represents the same meaning as in the formula (3) described in claim 12. ]

[In Formula (6), Y and Z represent the same meaning as in Formula (3) of Claim 12. ] The method according to claim 15 , wherein the aminating agent is aqueous ammonia.