JP2004315807A - Phthalocyanine pigment, ink, ink set, inkjet recording method using the ink or the ink set and coloring material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a phthalocyanine pigment having a good color tone as a cyan ink, excellent in light resistance, ozone resistance and moisture resistance, and suitable for inkjet recording. <P>SOLUTION: This specific phthalocyanine pigment has one or more unsubstituted sulfamoyl groups and substituted sulfamoyl groups as substituents. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a phthalocyanine dye, an ink, an ink set, an inkjet recording method using the ink or the ink set, a colored body, a method for improving ozone resistance, and a manufacturing method.

In recent years, as an image recording material, especially a material for forming a color image has been mainly used. Specifically, an ink jet recording material, a thermal transfer type image recording material, a recording material using an electrophotographic method, a transfer type halogen, Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. Color filters are used in LCDs and PDPs for displays, and in electronic parts such as CCDs for photographing equipment. In these color image recording materials and color filters, in order to reproduce or record a full-color image, dyes (dyes and pigments) of three primary colors of a so-called additive color mixture method or a subtractive color mixture method are used. In fact, there is no dye that has absorption characteristics capable of realizing the above and can endure 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 at the time of recording, and easy color recording. Ink jet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in response to an image information signal. , A method in which bubbles are generated in ink by heat to discharge droplets, a method using ultrasonic waves, and a method in which droplets are sucked and discharged by electrostatic force. Examples of inks suitable for inkjet recording include aqueous inks, oil-based inks, and solid (fused) inks.

For dyes used in inks suitable for such ink jet recording, the solubility or dispersibility in a solvent is good, high density recording is possible, the hue is good, light, heat, Strong against environmental active gases (oxidizing gases such as NOx and ozone, as well as SOx), excellent in durability against water and chemicals, good in fixability to recording materials, and resistant to bleeding. It is required that the ink be excellent in storage stability, not toxic, and be available at low cost. In particular, it has a good cyan hue and is excellent in light resistance (durability to light), ozone resistance (durability to ozone gas) and moisture resistance (durability under high humidity), and is also called a bronzing phenomenon (bronzing phenomenon). A cyan dye that does not cause) is strongly desired. The bronze phenomenon refers to a phenomenon in which the pigment becomes a metal flake on the surface of glossy paper or the like due to association of the pigment or poor absorption of the ink, and causes a glare. When this phenomenon occurs, the gloss, the print quality, and the print density are all inferior.

Representative skeletons of water-soluble cyan dyes used in inks suitable for ink-jet recording are phthalocyanine-based and triphenylmethane-based. The most widely reported and used representative phthalocyanine dyes include phthalocyanine derivatives classified into the following A to H.

A: Phthalocyanine dyes such as Direct Blue 86, Direct Blue 87, Direct Blue 199, Acid Blue 249 or Reactive Blue 71 [for example, a mixture of Cu-Pc- (SO ₃ Na) m = 1 to 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 dyes described in Patent Document 7 and the like [for example, Cu-Pc- (SO ₂ NR ₁ R ₂ ) n: n = 1 to 5]

G: Phthalocyanine-based dyes described in Patent Documents 8 and 9 [phthalocyanine-based dye in which substitution position of substituent is controlled, phthalocyanine-based dye having substitution type introduced at β-position]

H: Phthalocyanine dye having a pyridine ring described in Patent Document 10 and the like

A phthalocyanine dye represented by Direct Blue 86 or Direct Blue 199, which is widely used at present, is characterized by having superior light fastness compared to generally known magenta dyes and yellow dyes. The phthalocyanine dye has a greenish hue under acidic conditions, and is not preferable as a cyan ink. Therefore, when these dyes are used as cyan ink, it is preferable to use them under neutral to alkaline conditions. However, even if the ink is neutral to alkaline, the hue of the printed matter may significantly change when the recording material used is acidic paper.

Further, oxidizing gases such as nitrogen oxide gas and ozone, which are often taken up as an environmental problem in recent years, cause discoloration and decoloration to a greenish taste, and at the same time decrease the print density.

On the other hand, the triphenylmethane type has good hue, but is very poor in light fastness, ozone fastness and moisture fastness.

In the future, when the field of use is expanded and widely used for exhibitions such as advertisements, it is often exposed to light or active gas in the environment. Inexpensive dyes and inks that are resistant to environmental active gases (oxidizing gases such as NOx and ozone, as well as SOx, etc.) and that are inexpensive are increasingly desired. However, it is difficult to develop a cyan dye (for example, a phthalocyanine dye) and a cyan ink satisfying these requirements at a high level. So far, phthalocyanine dyes imparted with active gas resistance have been disclosed in Patent Documents 3, 8 to 11, and the like, but satisfy all qualities such as hue, light fastness, ozone fastness, and moisture fastness. Inexpensive cyan dyes and cyan inks have not yet been obtained. Therefore, the market has not yet been sufficiently satisfied.

JP-A-62-190273 JP-A-7-138511 JP-A-2002-105349 JP-A-5-17085 JP-A-10-140063 Japanese Patent Publication No. Hei 11-515048 JP-A-59-22967 JP-A-2000-303909 JP-A-2002-249677 JP 2003-34758 A JP-A-2002-80762

An object of the present invention is to solve the above-mentioned 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 and having excellent light fastness, ozone fastness and moisture fastness, and further suitable for inkjet using the phthalocyanine dye. To provide an ink and an ink jet recording method.

｛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。Ｒ₂、Ｒ₃、Ｒ₆、Ｒ₇、Ｒ₁₀、Ｒ₁₁、Ｒ₁₄、Ｒ₁₅は各々独立して式（２）で表される無置換スルファモイル基、式（３）で表される置換スルファモイル基又は水素原子を表わす。但し、Ｒ₂、Ｒ₃、Ｒ₆、Ｒ₇、Ｒ₁₀、Ｒ₁₁、Ｒ₁₄、Ｒ₁₅のうち少なくとも１つは無置換スルファモイル基、少なくとも１つは式（３）で表される置換スルファモイル基である。又、Ｒ₁、Ｒ₄、Ｒ₅、Ｒ₈、Ｒ₉、Ｒ₁₂、Ｒ₁₃、Ｒ₁₆は水素原子を表す。無置換スルファモイル基の数と置換スルファモイル基の数の和は２から４であり、且つ無置換スルファモイル基の数は１から３であり、置換スルファモイル基の数は１から３である。｝

｛式（３）中、Ｒ₁₇及びＲ₁₈はそれぞれ独立して水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロ環基、置換もしくは無置換のアルケニル基を表し、Ｒ₁₇及びＲ₁₈どうしが互いに連結して環を形成しても良い。但し、Ｒ₁₇及びＲ₁₈が共に水素原子の場合は除く。また、Ｒ₁₇及びＲ₁₈の少なくとも１つはイオン性親水性基を置換基として有する。｝
(２)(１）の式（１）において、ＭがＣｕである式（４）で表される、(１）に記載のフタロシアニン色素、

（式中、Ｒ₁〜Ｒ₁₆は式（１）と同じ意味を示す）。
(３)Ｒ₂とＲ₃、Ｒ₆とＲ₇、Ｒ₁₀とＲ₁₁、Ｒ₁₄とＲ₁₅の各組み合わせにおいて、それぞれの一方が水素原子であり、もう一方が式（２）で表される無置換スルファモイル基、式（３）で表される置換スルファモイル基又は水素原子であり、かつＲ₂、Ｒ₃、Ｒ₆、Ｒ₇、Ｒ₁₀、Ｒ₁₁、Ｒ₁₄、Ｒ₁₅のうち、少なくとも１つは無置換スルファモイル基であり、少なくとも１つは式（３）で表される置換スルファモイル基である(１）または（２）に記載のフタロシアニン色素、
(４)Ｒ₁₇及びＲ₁₈がそれぞれ独立して水素原子、アルキル基（スルホン酸基、カルボキシル基、水酸基、アルコキシ基、ジアルキルアミノ基、アリールアミノ基、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良い。）、フェニル基（スルホン酸基、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、ウレイド基、アルキル基、アルコキシ基、ニトロ基、シアノ基、ヘテロ環基、ハロゲン原子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良い。）、ナフチル基（スルホン酸基または水酸基で置換されても良い。）ベンジル基（スルホン酸基で置換されても良い。）、フェネチル基（スルホン酸で置換されても良い。）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色素、
(５)Ｒ₁₇が水素原子、カルボキシ（Ｃ１〜Ｃ５）アルキル基、（Ｃ１〜Ｃ５）アルキル基、ヒドロキシ（Ｃ１〜Ｃ５）アルキル基、またはスルホ（Ｃ１〜Ｃ５）アルキル基であり、Ｒ₁₈がスルホ（Ｃ１〜Ｃ５）アルキル基、カルボキシ（Ｃ１〜Ｃ５）アルキル基、スルホン酸基、カルボキシル基または水酸基を有するフェニル基、ジ（スルホ（Ｃ１〜Ｃ５）アルキル）アミノ（Ｃ１〜Ｃ５）アルキル基、スルホン酸基、カルボキシル基または水酸基を有するフェニル基で置換されたベンゾトリアゾリル基、スルホン酸基、カルボキシル基または水酸基を有するベンゾトリアゾール基で置換されたフェニル基、スルホン酸基または水酸基を有するナフチル基、スルホン酸基、カルボキシル基または水酸基を有するウラシル基、スルホン酸基、カルボキシル基または水酸基を有するトリアゾール基、スルホン酸基、カルボキシル基または水酸基を有するチアゾリル基、スルホン酸基、カルボキシル基または水酸基を有するベンゾチアゾリル基、スルホン酸基、カルボキシル基または水酸基を有するピリジン基、スルホン酸基、カルボキシル基または水酸基を有するベンズイミダゾリル基である(１）から（３）のいずれか一項に記載のフタロシアニン色素、
(６)式（１）の色素の含量が色素全体に対して少なくとも６０％以上である(１）に記載のフタロシアニン色素、
(７)式（１）が、式（５）で表されるフタロシアニン色素またはその塩に塩素化剤を反応させ、スルホン酸基をクロロスルホン基に変換した後、有機アミンの存在下にアミド化剤を反応させて得られてなる(１）から（５）のいずれか一項に記載のフタロシアニン色素、

｛式（５）中、Ｍは水素原子、金属元素、金属酸化物、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、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示す。ａ、ｂ、ｃ、ｄは０又は１であり、その和は２〜４の整数である。｝
(８)４−スルホフタル酸誘導体又は、４−スルホフタル酸誘導体と（無水）フタル酸誘導体を金属化合物の存在下に反応させることにより得られるスルホ金属フタロシアニン化合物またはその塩に塩素化剤を反応させ、スルホン酸基をクロロスルホン基に変換した後、アミド化剤と有機アミンを反応させて得られるフタロシアニン色素、
(９)色素成分として(１）から（８）のいずれか一項に記載のフタロシアニン色素を含有することを特徴とするインク、
(１０)有機溶剤を含有する(９）に記載のインク、
(１１)インクジェット記録用である(９）または（１０）に記載のインク、
(１２)色素濃度の異なる２種類以上のシアンインクを用いるインクジェットプリンタにおいて、そのうちの少なくとも１種類は(９）から（１１）のいずれか一項に記載のインクを用いることを特徴とするインクセット、
(１３)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、(９）から（１１）のいずれか一項に記載のインクまたは(１２）に記載の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、
(１４)被記録材が情報伝達用シートである(１３）に記載のインクジェット記録方法、
(１５)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(１４）に記載のインクジェット記録方法、
(１６)(９）から（１２）のいずれか一項に記載のインクまたはインクセットを含有する容器、
(１７)(１６）に記載の容器を有するインクジェットプリンタ、
(１８)(９）から（１２）のいずれか一項に記載のインクまたはインクセットで着色された着色体、
(１９)４−スルホフタル酸誘導体又は、４−スルホフタル酸誘導体と（無水）フタル酸誘導体を銅化合物の存在下に反応させることにより得られる化合物またはその塩に塩素化剤を反応させ、スルホン酸基をクロロスルホン基に変換した後、アミド化剤と有機アミンを反応させて得られることを特徴とするフタロシアニン色素の製造方法、
(２０)下記式（９）

｛式中、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し、ｌは０を含み１より小さく、ｍは１以上で３．７以下、ｎは０．３以上で３以下であり、ｌ、ｍ、ｎの合計は２以上４以下であり、Ｒ₁₇及びＲ₁₈はそれぞれ独立して水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロ環基、置換もしくは無置換のアルケニル基を表し、Ｒ₁₇及びＲ₁₈どうしが互いに連結して環を形成しても良い。但し、Ｒ₁₇及びＲ₁₈が共に水素原子の場合は除く。また、Ｒ₁₇及びＲ₁₈の少なくとも１つはイオン性親水性基を置換基として有する。｝
で表されるフタロシアニン色素において、β置換体が６０％以上であり、α位置換体が４０％以下であるフタロシアニン色素、
に関する。 The present inventors have studied in detail phthalocyanine dyes having good hue, high light resistance and high ozone resistance, and found that the above problem can be solved by using a specific phthalocyanine dye as a dye for ink. As a result, the present invention has been completed. More specifically, the present invention relates to a metal phthalocyanine dye represented by the following formula (1) having both a substituted sulfamoyl group and an unsubstituted sulfamoyl group at a specific substitution position (β-position: see below). It has a hue such as cyan and has excellent light resistance (durability to light), excellent moisture resistance (durability under high humidity), and excellent ozone resistance (durability to ozone gas), and completed the present invention. did. Hereinafter, the present invention will be described in detail. That is, the present invention
(1) a phthalocyanine dye represented by the formula (1) having at least one or more unsubstituted sulfamoyl groups and substituted sulfamoyl groups as substituents;

ＭIn the formula (1), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide or a metal halide. R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ are each independently an unsubstituted sulfamoyl group represented by the formula (2), a substituted group represented by the formula (3) Represents a sulfamoyl group or a hydrogen atom. However, at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ is an unsubstituted sulfamoyl group, and at least one is a substituted sulfamoyl represented by the formula (3). Group. R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ each represent a hydrogen atom. The sum of the number of unsubstituted sulfamoyl groups and the number of substituted sulfamoyl groups is 2 to 4, the number of unsubstituted sulfamoyl groups is 1 to 3, and the number of substituted sulfamoyl groups is 1 to 3. ｝

In the formula (3), R ₁₇ and R ₁₈ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents an aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group, and R ₁₇ and R ₁₈ may be linked to each other to form a ring. However, the case where both R ₁₇ and R ₁₈ are hydrogen atoms is excluded. Further, at least one of R ₁₇ and R ₁₈ has an ionic hydrophilic group as a substituent. ｝
(2) The phthalocyanine dye according to (1), wherein in formula (1) of (1), M is Cu and represented by formula (4):

(Wherein, R _{1 to} R ₁₆ have the same meaning as in formula (1)).
(3) In each combination of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , R ₁₄ and R _{15, one} of each is a hydrogen atom, and the other is represented by the formula (2). An unsubstituted sulfamoyl group, a substituted sulfamoyl group represented by the formula (3) or a hydrogen atom, and among R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ A phthalocyanine dye according to (1) or (2), wherein at least one is an unsubstituted sulfamoyl group, and at least one is a substituted sulfamoyl group represented by the formula (3):
(4) R ₁₇ and R ₁₈ each independently represent a hydrogen atom, an alkyl group (a group consisting of a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkoxy group, a dialkylamino group, an arylamino group, an aryl group, a halogen atom, and a cyano group) And a phenyl group (sulfonic acid group, carboxyl group, hydroxyl group, dialkylamino group, arylamino group, acetylamino group, ureido group, alkyl group, alkoxy group, nitro group) , A cyano group, a heterocyclic group, or a halogen atom, and may be substituted with one or more substituents.), A naphthyl group (may be substituted with a sulfonic acid group or a hydroxyl group). ) Groups (1) to (3) which are a benzyl group (may be substituted with a sulfonic acid group) and a phenethyl group (may be substituted with a sulfonic acid group). Phthalocyanine dyes according to any one of,
(5) R ₁₇ is a hydrogen atom, a carboxy (C1 to C5) alkyl group, (C1 to C5) alkyl group, hydroxy (C1 to C5) alkyl group or a sulfo (C1 to C5) alkyl group, and R ₁₈ A sulfo (C1-C5) alkyl group, a carboxy (C1-C5) alkyl group, a sulfonic group, a phenyl group having a carboxyl group or a hydroxyl group, a di (sulfo (C1-C5) alkyl) amino (C1-C5) alkyl group, Naphthyl having a benzotriazolyl group substituted by a sulfonic group, a carboxyl group or a phenyl group having a hydroxyl group, a phenyl group substituted by a benzotriazole group having a sulfonic group, a carboxyl group or a hydroxyl group, a sulfonic group or a hydroxyl group Group, sulfonic acid group, uracil group having carboxyl group or hydroxyl group, sulfonic acid group, Triazole group having a boxyl group or a hydroxyl group, sulfonic acid group, thiazolyl group having a carboxyl group or a hydroxyl group, sulfonic acid group, benzothiazolyl group having a carboxyl group or a hydroxyl group, sulfonic acid group, pyridine group having a carboxyl group or a hydroxyl group, sulfonic acid The phthalocyanine dye according to any one of (1) to (3), which is a benzimidazolyl group having a carboxyl group or a hydroxyl group.
(6) The phthalocyanine dye according to (1), wherein the content of the dye of the formula (1) is at least 60% or more of the whole dye.
(7) The phthalocyanine dye represented by formula (1) or a salt thereof is reacted with a chlorinating agent to convert a sulfonic acid group into a chlorosulfone group, and then amidated in the presence of an organic amine. The phthalocyanine dye according to any one of (1) to (5), which is obtained by reacting an agent,

｛In the formula (5), M represents a hydrogen atom, a metal element, a metal oxide, or a metal halide, and L represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion or an ammonium ion of an organic amine, respectively. . a, b, c, and d are 0 or 1, and the sum thereof is an integer of 2 to 4. ｝
(8) reacting a 4-sulfophthalic acid derivative or a sulfometal phthalocyanine compound obtained by reacting a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a metal compound with a chlorinating agent, After converting the sulfonic acid group to a chlorosulfone group, a phthalocyanine dye obtained by reacting an amidating agent with an organic amine,
(9) An ink comprising the phthalocyanine dye according to any one of (1) to (8) as a dye component,
(10) The ink according to (9), which contains an organic solvent.
(11) The ink according to (9) or (10), which is for inkjet recording.
(12) An ink set comprising an ink jet printer using two or more types of cyan inks having different dye concentrations, wherein at least one of the inks uses the ink according to any one of (9) to (11). ,
(13) In an ink jet recording method for recording on a recording material by discharging ink droplets in accordance with a recording signal, the ink according to any one of (9) to (11) or the ink according to (12). An inkjet recording method, characterized by using a set,
(14) The inkjet recording method according to (13), wherein the recording material is an information transmission sheet.
(15) The ink jet recording method according to (14), wherein the information transmission sheet is a surface-treated sheet and has an ink image receiving layer containing white inorganic pigment particles on a support.
(16) A container containing the ink or the ink set according to any one of (9) to (12),
(17) An inkjet printer having the container according to (16),
(18) A colored body colored with the ink or the ink set according to any one of (9) to (12),
(19) A chlorinating agent is reacted with a compound obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a copper compound to react with a sulfonic acid Is converted to a chlorosulfone group, a method for producing a phthalocyanine dye, which is obtained by reacting an amidating agent with an organic amine,
(20) The following equation (9)

中 In the formula, M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide or a metal halide, 1 is less than 1 including 0, m is 1 or more and 3.7 or less, and n is 0.1 or less. 3 or more and 3 or less, the sum of l, m and n is 2 or more and 4 or less, and R ₁₇ and R ₁₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclo group. Represents an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group, wherein R ₁₇ and R ₁₈ are linked to each other May be formed. However, the case where both R ₁₇ and R ₁₈ are hydrogen atoms is excluded. At least one of R ₁₇ and R ₁₈ has an ionic hydrophilic group as a substituent. ｝
In the phthalocyanine dye represented by the formula, a phthalocyanine dye having 60% or more of β-substituted product and 40% or less of α-substituted product,
About.

The ink using the phthalocyanine dye of the present invention has a good hue as a cyan ink and is excellent in light fastness, ozone fastness and moisture fastness. Further, there is no crystal precipitation, physical property change, color change and the like after long-term storage, and the storage stability is good. Further, when used together with other magenta ink and yellow ink, it is possible to color tone in a wide visible region. Therefore, the cyan ink using the phthalocyanine dye of the present invention is extremely useful as an ink for inkjet recording.

The present invention will be described in detail. The ink suitable for inkjet recording of the present invention is characterized by containing the phthalocyanine dye of the formula (1). The present invention provides a phthalocyanine dye obtained by converting a sulfone group into a chlorosulfone group using a compound reported in Patent Document 8 as a raw material, and then reacting with an amidating agent in the presence of an organic amine, that is, a compound represented by the formula (1): It has been found that an ink using a phthalocyanine dye having an unsubstituted sulfamoyl group and a substituted sulfamoyl group introduced at a specific substitution position (β-position) of a phthalocyanine ring has extremely excellent resistance to ozone gas. .

In general, the phthalocyanine derivative is inevitably produced at the time of its synthesis, by substituting the substituents R (n = 1 to 16) in the following formula (1) at the positions on the benzene nucleus to which R _{1 to} R ₁₆ are bonded. In some cases, isomers (defined as positions 1 to 16) are included, but these substituted positional isomers are often regarded as the same derivative without being distinguished from each other.

(In the formula (1), M and R _{1 to} R ₁₆ have the same meanings as described above.) In this specification, for convenience, three types of phthalocyanine derivatives having different substitution positions are defined as (1) β- It is classified into position-substituted type, (2) α-position-substituted type, and (3) α-, β-position mixed-substituted type, and is used to describe phthalocyanine derivatives having different substitution positions.
In the following description, the substitution positions at the 1-position to the 16-position refer to the positions on the benzene nucleus where the substituents R _{1 to} R ₁₆ of the above formula (1) are bonded, respectively. The same shall apply.

(1) β-position-substituted type: (phthalocyanine dye having a specific substituent at position 2 and / or 3, 6 and / or 7, 10 and / or 11, 14 and / or 15)
(2) α-position-substituted type: (phthalocyanine dye having a specific substituent at 1- and / or 4-, 5- and / or 8-, 9- and / or 12-, 13- and / or 16-position)
(3) α, β-position mixed substitution type: (phthalocyanine dye having a specific substituent at any position of positions 1 to 16)
The phthalocyanine dye of the present invention represented by the formula (1) belongs to the above β-position substituted type.

The above-mentioned phthalocyanine dyes of β-position substitution type, α-position substitution type, α, β-position mixed substitution type are obtained by decomposing phthalic acid derivatives by nitric acid or the like, and examining substitution positions by NMR. Can be determined.
That is, when the phthalocyanine dye of the β-position is decomposed, the phthalic acid derivative of the 4-position is decomposed, and when the phthalocyanine dye of the α-position is decomposed, the phthalic acid derivative of the 3-position is mixed with the α, β-position. When the substituted phthalocyanine dye is decomposed, 3- and 4-substituted phthalic acid derivatives are obtained.

In the above formula (1), M represents a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. 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, for example, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) ₂ , and AlOH. Further, examples of the metal halide include SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, ZrCl, and AlCl. Among them, 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 an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group and the like is not particularly limited as long as the object of the present invention is achieved. Usually, they have about 1 to 16, preferably 1 to 12, more preferably 1 to 6, and even about 1 to 4 carbon atoms. However, about a cycloalkyl group, it is usually about 3 to 12, preferably about 5 to 8. When these have a substituent, the type of the substituent is not particularly limited as long as the object of the present invention is achieved. Preferred substituents on the carbon chain of these groups include, for example, a sulfonic acid group and a group derived therefrom (such as a sulfonamide), a carboxyl group and a group derived therefrom (such as a carboxylic acid ester group), a phosphate group and Examples thereof include a group derived therefrom (such as a phosphate group), a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, a halogen atom, and a cyano group.
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. Preferred substituents on the aryl group include, for example, those listed above as preferred substituents on the carbon chain, and urenoid groups, nitro groups, heterocyclic groups, and the like.

In the formula (3), R ₁₇ and R ₁₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted Represents a heterocyclic group or a substituted or unsubstituted alkenyl group, and R ₁₇ and R ₁₈ may be linked to each other to form a ring; However, the case where both R ₁₇ and R ₁₈ are hydrogen atoms is excluded. Further, at least one of R ₁₇ and R ₁₈ has an ionic hydrophilic group as a substituent. As the ionic hydrophilic group, an anionic hydrophilic group is preferable, and examples thereof include a sulfonic acid group, a carboxyl group, and a phosphate group. These ionic hydrophilic groups may be in a free form, or may be an alkali metal salt, an alkaline earth metal salt, an onium ion salt or an ammonium salt of an organic amine. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include calcium, magnesium and the like. As the organic amine, examples of the alkylamine include lower alkylamines having 1 to 4 carbon atoms such as methylamine and ethylamine. Examples of the alkanolamine include mono, di or tri (lower alkanol having 1 to 4 carbon atoms) amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine. Preferred are salts of ammonium, sodium, potassium, lithium, monoethanolamine, diethanolamine, trienolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

Examples of the substituted or unsubstituted alkyl group include an alkyl group having 1 to 12 carbon atoms. Examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid 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), a halogen atom, and a cyano group. No. Among them, a sulfonic acid group, a carboxyl group, a phosphoric acid group and a hydroxyl group are preferred.

Examples of the substituted or unsubstituted cycloalkyl group include a cycloalkyl group having 3 to 12 carbon atoms. Preferably a C5-8 cycloalkyl group is mentioned. Examples of the substituent on the cycloalkyl ring include, for example, a sulfonic 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, and a halogen. Atom and cyano group. Among them, a sulfonic acid group, a carboxyl group, a phosphoric acid group and a hydroxyl group are preferred.

  The carbon number of the alkyl group in the alkyl group (aralkyl group) substituted with the aryl group is preferably about 1 to 12. The aralkyl group may have a substituent, and examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, and an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group. Good), a ureido group, an alkyl group, an alkoxy group, a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Among them, a sulfonic acid group, a carboxyl group, a phosphoric acid group and a hydroxyl group are preferred.

  Examples of the substituted or unsubstituted aryl group include a phenyl group and a naphthyl group. Examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid 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, and a nitro group. Group, a cyano group, a heterocyclic group, and a halogen atom. Among them, a sulfonic acid group, a carboxyl group, a phosphoric acid group and a hydroxyl group are preferred.

  The substituted or unsubstituted heterocyclic group is preferably a 5- or 6-membered ring, which may be further condensed. Further, it may be an aromatic hetero ring or a non-aromatic hetero ring. 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, Oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These hetero rings may have a substituent, and examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, and an amino group (an alkyl group, an aryl group, and an acetyl group. May be substituted.), A ureido group, an alkyl group, an alkoxy group, a nitro group, a cyano group, and a halogen atom.

  Examples of the substituted or unsubstituted alkenyl group include alkenyl groups having 1 to 12 carbon atoms. Examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid 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. Among them, a sulfonic acid group, a carboxyl group, a phosphoric acid group and a hydroxyl group are preferred.

In the formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently an unsubstituted sulfamoyl group represented by the formula (2), ) Represents a substituted sulfamoyl group or a hydrogen atom, and at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ is an unsubstituted sulfamoyl group; One is a substituted sulfamoyl group. _{R 1, R 4, R 5} , R 8, R 9, R 12, R 13, R 16 represents a hydrogen atom. The sum of the number of unsubstituted sulfamoyl groups and the number of substituted sulfamoyl groups is 2 to 4, the number of unsubstituted sulfamoyl groups is 1 to 3, and the number of substituted sulfamoyl groups is 1 to 3.
In the combination of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R ₁₅ , one is preferably a hydrogen atom and the other is preferably an unsubstituted sulfamoyl group (—SO ₂ NH ₂ ) or a substituted sulfamoyl group represented by the formula (3), and at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ is unsubstituted At least one of the sulfamoyl groups is a substituted sulfamoyl group represented by the formula (3).

In the phthalocyanine dye of the present invention represented by the formula (1), the ratio of the unsubstituted sulfamoyl group represented by the formula (2) to the substituted sulfamoyl group represented by the formula (3) is 1: 3 to 3: 1. Is a compound.
When the ratio of the unsubstituted sulfamoyl group represented by the formula (2) is high, the ozone resistance is high, but the water solubility is low and the bronze phenomenon tends to occur. Conversely, when the ratio of the substituted sulfamoyl group represented by the formula (3) is high, the water solubility is high, and the bronze phenomenon is less likely to occur, while the ozone resistance tends to be lower. Therefore, the ratio of the unsubstituted sulfamoyl group represented by the formula (2) to the substituted sulfamoyl group represented by the formula (3) is appropriately adjusted according to the type of the substituted sulfamoyl group represented by the formula (3). What is necessary is to select a well-balanced ratio.
Specific examples of the combination of M and the formula (3) in the phthalocyanine dye represented by the formula (1) of the present invention are shown in Tables 1 to 5, but the phthalocyanine dye used in the present invention is limited to the following examples. It is not done. In the table, the formula (3) is described in the form of a free acid.

The phthalocyanine dye of the present invention is a compound obtained by reacting 4-sulfophthalic acid derivatives with each other or a 4-sulfophthalic acid derivative and a (phthalic anhydride) phthalic acid derivative in the presence of a metal compound (β-substituted sulfophthalocyanine). ) Is reacted with a chlorinating agent to convert a sulfonic acid group into a chlorosulfone group, and then reacted with an amidating agent and an organic amine. The 4-sulfophthalic acid derivative used as a raw material generally contains about 15 to 25% by weight of an impurity sulfonated at the 3-position as an impurity, and the α-substituted product derived therefrom is mixed into the target phthalocyanine dye. In order to further enhance the effects of the present invention (especially in order to obtain an ink having high ozone resistance), it is preferable to use a raw material having a low content of impurities sulfonated at the 3-position.
In the target phthalocyanine dye, a chlorosulfone group partially decomposed during the reaction is mixed into the reaction product, but this does not cause any problem. The obtained dye is represented by the following formula (9), and it is considered that the β-substituted substance is a main component, that is, at least 60%, preferably 70% or more, and more preferably 75% or more.

(In the formula (9), M, R ₁₇ and R ₁₈ have the same meanings as described above. L is less than 1 including 0, preferably 0.7 or less, more preferably 0.5 or less, most preferably 0.3 or less, n is 0.3 or more, preferably 0.7 or more and 3 or less, m is 1 or more and 3.7 or less, and the total of l, m, and n is 2 or more and 4 or less. The values of l, m, and n indicate average values in the mixture.)

  In producing the phthalocyanine dye of the present invention, the ratio (molar ratio) of the amidating agent and the organic amine corresponding to the substituted sulfamoyl group represented by the formula (3) is replaced with the unsubstituted sulfamoyl introduced into the phthalocyanine dye. It is preferable to use the sulfamoyl at a ratio such that the ratio is 1: 3 to 3: 1. When the ratio of unsubstituted sulfamoyl groups (reaction ratio of the amidating agent) is high, the ozone resistance of the image recorded with the obtained ink containing the phthalocyanine dye is increased, while the water solubility is low and the bronze phenomenon is likely to occur. There is a tendency. Conversely, when the ratio of the organic amine is high, the obtained phthalocyanine dye has high water solubility, and the bronzing phenomenon is less likely to occur, while the ozone resistance tends to be lower. Therefore, the ratio between the amidating agent and the organic amine may be appropriately adjusted according to the type of the organic amine to be used, and a well-balanced ratio may be selected.

The method for producing the compound of the formula (1) of the present invention will be described.

First, a metal phthalocyanine sulfonic acid represented by the formula (5) is synthesized. As described above, in the phthalocyanine dye of the present invention, an α-position-substituted product derived from a raw material is produced as a by-product, but in the description of the production method, the β-position-substituted product of the main component will be described.
Formula (5) can be synthesized, for example, by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a catalyst and a metal compound.
By changing the molar ratio of the reaction between 4-sulfophthalic acid and (phthalic anhydride), the number of sulfone groups, that is, the number of ad can be adjusted. The 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 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, the addition of urea is essential. The amount of urea used is 5 to 100 times the molar amount of 1 mol of the 4-sulfophthalic acid derivative.

［式（５）中、Ｍ、Ｌ、ａ、ｂ、ｃ、ｄは前記と同じ意味を表す。］

[In the formula (5), M, L, a, b, c, and d represent the same meaning as described above. ]

The reaction is usually performed in the presence of a solvent, and an organic solvent having a boiling point of 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, boric acid, and the like. The addition amount is 0.001 to 1 mole per 1 mole of the 4-sulfophthalic acid derivative.

As the metal compound, 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, carboxylate, sulfate, nitrate, acetylacetonate, carbonyl compound, complex And the like. Examples include copper chloride, copper bromide, nickel chloride, nickel acetate, cobalt chloride, cobalt acetate, cobalt acetylacetonate and the like. The amount of the metal compound to be used is 0.15 to 0.35 mol per mol of the 4-sulfophthalic acid derivative or the total of 1 mol of the 4-sulfophthalic acid derivative and the (unsubstituted) phthalic acid derivative.

The reaction temperature is usually from 100 to 290 ° C, preferably from 130 to 270 ° C. The reaction time varies depending on the reaction temperature, but is usually 1 to 8 hours. After completion of the reaction, the product is obtained in the form of metal phthalocyanine tetrasulfonic acid or a salt thereof by filtration, salting out (or aciding out), and drying. In order to obtain a free acid, for example, acid precipitation may be performed. In addition, salt formation is carried out by salting out, or when a desired salt cannot be obtained by salting out, for example, a usual salt exchange method in which a desired organic or inorganic base is added to a free acid is used. Just fine.

Further, a copper phthalocyanine tetrasulfonic acid or a salt thereof in which M is copper is synthesized by the method described in Patent Document 8, and a compound in which a, b, c, and d in the above formula (5) are represented by 1 is In a sulfolane solvent, 4-sulfophthalic acid (1 mol), copper (II) chloride (0.3 mol), ammonium phosphomolybdate (0.003 mol), urea (6 mol), ammonium chloride (0.5 mol) ) At 180 ° C. for 6 hours to obtain copper phthalocyanine tetrasulfonic acid represented by the formula (5). The reactivity differs depending on the type and amount of the 4-sulfophthalic acid derivative, metal compound, solvent, catalyst and the like, and is not limited to the above.

  By reacting a phthalocyanine sulfonic acid or a salt thereof represented by the formula (5) with a chlorinating agent in a solvent such as an organic solvent, sulfuric acid, fuming sulfuric acid or chlorosulfonic acid, the compound is represented by the formula (7). Metal phthalocyanine sulfonic acid chloride is obtained. The chlorinating agent is preferably used in excess with respect to the sulfonic acid group of phthalocyanine sulfonic acid or a salt thereof, and the molar ratio to the sulfonic acid group is about 1 to 10 times, preferably 1.5 times or more. Organic solvents used in the reaction include, but are not limited to, benzene, toluene, nitrobenzene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide. Examples of the chlorinating agent include chlorosulfonic acid, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like, but are not limited thereto. Further, in the phthalocyanine dye of the present invention, some chlorinated impurities may be generated in the phthalocyanine nucleus and may be mixed into the reaction product.

〔式中、Ｍ、ａ、ｂ、ｃ、ｄは前記と同じ意味を表す。〕

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

Next, the target compound is obtained by reacting the obtained phthalocyanine tetrasulfonic acid chloride, the corresponding organic amine and the amidating agent in an aqueous solvent at a pH of usually 6 to 10, usually at 5 to 70 ° C. and usually for 1 to 20 hours. Can be The amount of the amidating agent and the organic amine to be used is preferably at least equimolar to the sulfonic acid chloride group of the phthalocyanine sulfonic acid chloride in total (molar ratio), usually 1 to 20 times, preferably 1.5 times. It is about 5 times mol. The proportion of the organic amine may be used according to the proportion of the substituted sulfamoyl group of the target compound.
Examples of the amidating agent used for the reaction include, but are not limited to, ammonium salts such as ammonium chloride and ammonium sulfate, urea, aqueous ammonia, and ammonia gas.

The amount of the organic amine to be used is usually 1 mole or more of the theoretical value per mole of the phthalocyanine dye, but it depends on the reactivity and reaction conditions of the organic amine, and is not limited thereto. .

Further, in the phthalocyanine dye of the present invention, an impurity in which a phthalocyanine ring (Pc) forms a dimer (for example, Pc-L-Pc) or a trimer via a divalent linking group (L) is partially generated. , May be mixed into the reaction product, and a plurality of L present at that time may be the same or different.

Examples of the divalent linking group represented by L include a sulfonyl group (—SO ₂ —) and —SO ₂ —NH—SO ₂ —. Further, the linking group may be a group formed by combining these.

The phthalocyanine dye of the present invention thus obtained can be separated by filtration or the like after acid precipitation or salting out. The salting out is preferably carried out, for example, in the range of acidic to alkaline, preferably in the range of pH 1 to 11. The temperature at the time of salting out is not particularly limited, but it is generally preferable to heat to 40 to 80 ° C, preferably 50 to 70 ° C, and then add salt and the like for salting out.

The phthalocyanine dyes represented by the formulas (1), (2) and (3) of the present invention, which are synthesized by the above method, are obtained in the form of a free acid or a salt thereof. In order to obtain a free acid, for example, acid precipitation may be performed. In addition, salt formation is carried out by salting out, or when a desired salt cannot be obtained by salting out, for example, a usual salt exchange method in which a desired organic or inorganic base is added to a free acid is used. Just fine.

The cyan ink of the present invention contains the phthalocyanine dye of the formula (1) 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, and the content of SO ₄ ^2-, etc. anions preferably have less, measure of the content thereof, in a phthalocyanine dye Cl ^{- -} Cl contained and SO ₄ 5 wt% or less as the total content of ^2-, preferably Is 3% by mass or less, more preferably 1% by mass or less, and 1% by mass or less in the ink. In order to produce the phthalocyanine dye of the present invention having a small amount of Cl ^- and SO ₄ ^2- , for example, a usual method using a reverse osmosis membrane or a dried product or a wet cake of the phthalocyanine dye of the present invention is stirred in a mixed solvent of alcohol and water. Then, desalting may be performed by a method such as filtration and drying. 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, at the time of desalting treatment with alcohol, a method of heating to near the boiling point of the alcohol to be used, followed by cooling and desalting may be employed. Cl ^- and SO ₄ content of ² is measured by an ion chromatography.

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 and metals (cations) such as calcium and silica contained in the phthalocyanine dye is used. Is preferable (excluding the metal (M in the formula (1)) contained in the phthalocyanine skeleton). The standard of the content is, for example, about 500 ppm or less for heavy metals (ions) such as zinc and iron and metals (cations) such as calcium and silica in a purified and dried phthalocyanine dye. The contents of heavy metals (ions) and metals (cations) are measured by ion chromatography, atomic absorption, or ICP (Inductively Coupled Plasma) emission spectrometry.

The phthalocyanine dye of the formula (1) is 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 concentration ink contains 0.1 to 2.5% by mass of the phthalocyanine dye of the present invention.

The ink of the present invention is prepared using water as a medium. The ink of the present invention contains 0.3 to 6% by mass of the mixture of the compound of the formula (1) or the salt thereof satisfying the above conditions and obtained as described above. If necessary, the ink of the present invention further contains a water-soluble organic solvent within a range that does not impair the effects of the present invention. The water-soluble organic solvent is used as a dye dissolving agent, an anti-drying agent (wetting agent), a viscosity adjusting agent, a penetration enhancer, a surface tension adjusting agent, an antifoaming agent, and the like. Other ink preparations include, for example, preservatives and fungicides, pH adjusters, chelating agents, rust inhibitors, ultraviolet absorbers, viscosity adjusters, dye dissolving agents, anti-fading agents, emulsion stabilizers, surface tension adjusters, Known additives such as an antifoaming agent, a dispersant, and a dispersion stabilizer are exemplified. The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass based on the whole ink, and the ink preparation agent is 0 to 20% by mass, preferably 0 to 15% by mass based on the whole ink. Good to use. The balance other than the above is water.

Examples of the water-soluble organic solvent that can be used in the present invention include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol, and N, N-dimethyl. Carboxylic acid amides such as formamide or N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2- Heterocyclic ketones such as ON, 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, 1,2- Has (C2-C6) alkylene units such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, and polypropylene glycol. Monomers, oligomers or polyalkylene glycols or thioglycols, 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 Polyvalent such as ethylene glycol monomethyl ether or triethylene glycol monoethyl ether (C1 -C4) alkyl ethers of alcohol, gamma-butyrolactone or dimethyl sulfoxide and the like.

  In the ink of the present invention, preferable examples of the water-soluble organic solvent include mono- or polyhydric alcohols having 3 to 8 carbon atoms and 2-pyrrolidone which may have alkyl substitution having 1 to 3 carbon atoms. As the hydric alcohol, those having 2 to 3 hydroxy groups are preferable. Specific examples include isopropanol, glycerin, mono, di or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, butanol, and more preferably isopropanol, glycerin, diethylene glycol, and 2-pyrrolidone. is there. These water-soluble organic solvents are used alone or as a mixture.

Examples of the antiseptic / antifungal agent include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallyl sulfone-based, iodopropagyl-based, N-haloalkylthio-based, benzthiazole-based, nitritolyl-based, pyridine-based, and 8- Oxyquinoline type, benzothiazole type, isothiazoline type, dithiol type, pyridine acid type, nitropropane type, organic tin type, phenol type, quaternary ammonium salt type, triazine type, thiadiazine type, anilide type, adamantane type, dithiocarbamate type, Brominated indanone compounds, benzyl bromoacetate compounds, inorganic salt compounds and the like can be mentioned. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine acid compound include sodium 2-pyridinethiol-1-oxide, and examples of the inorganic salt compound include sodium acetate anhydride. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, -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 and the like. No. Other preservatives and fungicides include sodium sorbate sodium benzoate and the like (for example, Proxel GXL (S) and 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 in 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, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, and alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate Carbonates and the like.

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

As the ultraviolet absorber, for example, a compound that absorbs ultraviolet light and emits fluorescence represented by a benzophenone-based compound, a benzotriazole-based compound, a cinnamic acid-based compound, a triazine-based compound, a stilbene-based compound, or a benzoxazole-based compound, so-called fluorescence Brighteners can also be used.

Examples of the viscosity modifier include a water-soluble polymer compound in addition to a water-soluble organic solvent, such as polyvinyl alcohol, a cellulose derivative, polyamine, and polyimine.

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

The anti-fading agent is used for the purpose of improving the storability of an image. As an anti-fading agent, various organic and metal complex-based anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Complexes and zinc complexes.

Examples of the surface tension modifier include surfactants, for example, anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants. Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acylmethyl taurine salts, alkyl sulfate polyoxyalkyl ethers Sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl alcohol sulfate, alkyl phenol phosphate, alkyl phosphate, alkyl allyl sulfonate, diethyl sulfosuccinate And diethylhexylsulfosuccinate dioctylsulfosuccinate. Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly-4-vinylpyridine derivative. Examples of the amphoteric surfactant include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amide propyldimethylaminoacetate betaine, polyoctyl polyaminoethylglycine, 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 and polyoxyallylalkyl alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquis Esters such as oleate, polyoxyethylene monooleate and polyoxyethylene stearate, 2,4,7, Acetylene glycols such as -tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, Olfin STG, etc., manufactured by Nissin Chemical Co., Ltd.). These ink preparations are used alone or as a mixture. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, and more preferably 25 to 60 mN / m. The viscosity of the ink of the present invention is preferably 30 mPa · s or less. It is more preferable to adjust the pressure to 20 mPa · s or less.

As the defoaming agent, a fluorine-based or silicone-based compound is used as needed.

In producing the ink of the present invention, there is no particular limitation on the order in which the respective chemicals are dissolved. In preparing the ink, the water used is preferably an ion-exchanged water or a water having a small amount of impurities such as distilled water. Further, if necessary, fine filtration may be performed using a membrane filter or the like to remove impurities. When used as an ink for an inkjet printer, it is preferable to perform fine filtration. The pore size of the filter for microfiltration is usually 1 micron to 0.1 micron, preferably 0.8 micron to 0.2 micron.

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

Various dyes can be used as the dye of the applicable yellow ink. For example, aryl or hetenylazo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone or pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); Azomethine dyes having open-chain active methylene compounds and the like; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and the like. Examples include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

Various dyes can be used as the dye of the applicable magenta ink. 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. Methine dyes; carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; and condensed polycyclic dyes such as dioxazine dyes.

Each of the above-mentioned dyes may exhibit each color of yellow, magenta and cyan only after a part of the chromophore dissociates, and in this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Or an organic cation such as a pyridinium or quaternary ammonium salt, or a polymer cation having these in a partial structure. Examples of applicable black dyes include disazo, trisazo, and tetraazo dyes, as well as carbon black dispersions.

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

The ink-jet recording method of the present invention provides energy to the ink adjusted as described above to obtain a known image-receiving material, that is, plain paper, resin-coated paper, inkjet-only paper, glossy paper, glossy film, electrophotographic paper, fiber It forms images on paper and cloth (cellulose, nylon, wool, etc.), glass, metal, ceramics, leather and the like.

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 gloss, water resistance, or improving weather resistance. The timing of applying the polymer latex to the recording material may be before, after, or simultaneously with the application of the colorant. May be in the ink, or may be used as a liquid material of the polymer latex alone.

Hereinafter, a recording material (particularly, recording paper and recording film) used for performing inkjet printing using the ink of the present invention will be described. The support in recording paper and recording film is composed of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP and CGP, waste paper pulp such as DIP, etc. Additives such as a binder, a sizing agent, a fixing agent, a cationic agent, and a paper strength agent are mixed, and those manufactured by various apparatuses such as a fourdrinier paper machine and a circular net paper machine can be used. In addition to these supports, any of synthetic paper and plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm, and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with an ink receiving layer and a back coat layer as they are, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, and then providing an ink receiving layer and a back coat layer. Further, the support may be subjected to a flattening treatment using a calender such as a machine calender, a TG calender, and a soft calender. In the present invention, a paper and a plastic film laminated on both sides with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and a copolymer thereof) on both sides are more preferably used. It is preferable to add a white pigment (for example, titanium oxide, zinc oxide) or a coloring dye (for example, cobalt blue, ultramarine, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support may contain a pigment or an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate; and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and a synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, both silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include aqueous solutions of polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. And water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer. The ink receiving layer may contain a mordant, a water-proofing agent, a lightfastness improving agent, a surfactant, and other additives in addition to the pigment and the aqueous binder.

As the mordant added to the ink receiving layer, for example, a polymer mordant is used.

The water-proofing agent is effective for making the image water-resistant, and as such a water-proofing agent, a cationic resin is particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, and the like. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably from 1 to 15% by mass, more preferably from 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, and benzophenone-based and benzotriazole-based ultraviolet absorbers. Of these, zinc sulfate is preferred.

The surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, ethylene tetrafluoride resin). Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, fluorescent brighteners, preservatives, pH adjusters, matting agents, hardeners, and the like. . The ink receiving layer may be a single layer or two layers.

A recording paper and a recording film may be provided with a back coat layer. Examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, and other white inorganic pigments Organic pigments such as styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

Examples of the aqueous binder contained in the back coat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose. And water-soluble polymers such as hydroxyethylcellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

A polymer latex may be added to the constituent layers (including the back coat layer) of the inkjet recording paper and the recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

  These recording papers and recording films are generally called inkjet-only papers, glossy papers or glossy films, and include, for example, Pictorico (trade name: manufactured by Asahi Glass Co., Ltd.), color BJ paper, high-grade exclusive paper, color BJ Photo film sheet, Super Photo Paper, Professional Photo Paper (trade names: all manufactured by Canon Inc.), Color Image Jet Paper (trade name: manufactured by Sharp Corp.), PM Photo Paper, Glossy Film for Super Fine (product) Name: Both are manufactured by Epson Corporation, and Pictafine (trade name: manufactured by Hitachi Maxell, Ltd.). In particular, the ink jet recording method using the ink of the present invention works particularly effectively on recording paper and recording films having an ink image receiving layer containing white inorganic pigment particles on a support as a recording material. Of course, it can also be used for plain paper.

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

In order to record on a 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 an ink jet printer, and recording may be performed on the recording material by a usual 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 invention does not settle 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 inks according to the invention do not change their physical properties under constant recirculation for a relatively long period of time with continuous ink jet printers or even in intermittent use with on demand ink jet printers.

  The inks of the present invention are vivid cyan when using the preferred dyes. Further, it is possible to obtain a recorded matter which is particularly excellent in ozone resistance, light resistance and water resistance. By using as a set of dark and light cyan inks, it is possible to obtain a recorded matter having further excellent ozone resistance, light resistance and water resistance. Also, when used with other yellow, magenta, and other inks such as green, red, orange, and blue as needed, it can produce colors in a wide visible region, and has excellent ozone resistance and light resistance. It is possible to obtain a recorded matter having excellent properties and water resistance.

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

Example 1
In the formula (1), M has copper, two unsubstituted sulfamoyl groups at the β-position and two substituted sulfamoyl groups of the formula (3), and in the formula (3), R ₁₇ is a 2-sulfoethyl group and R ₁₈ is Synthesis of Compounds that are Hydrogen Atoms (1) Synthesis of Copper Sodium Phthalocyanine Tetrasulfonate Tetrasodium Salt (β-Substituted Type) (M is Cu, a, b, c, d are all 1, L is Na A compound of formula (5)
40 parts of sulfolane was added to a four-necked flask equipped with a cooling tube, and the temperature was raised to 180 ° C. in 1 hour. Thereto, 40 parts of monosodium 4-sulfophthalate, 4.5 parts of ammonium chloride, 55 parts of urea, 55 parts of molybdenum 0.5 parts of ammonium acid and 6 parts of copper (II) chloride were added, and the mixture was stirred at the same temperature for 6 hours. After the reaction solution was cooled to 40 ° C., the target substance was filtered with Nutsche and washed with 400 parts of methanol. Subsequently, 300 parts of water was added to the obtained wet cake, the pH was adjusted to 11 with a 48% aqueous sodium hydroxide solution, and the mixture was stirred at 80 ° C for 1 hour. Then, a 35% hydrochloric acid aqueous solution was added to the mixture to adjust the pH to 3, while stirring, 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 the mixture was stirred for 1 hour. The precipitated crystals were separated by filtration, washed with 300 parts of a 70% aqueous methanol solution, and dried, to obtain a β-substituted copper phthalocyanine tetrasulfonic acid of formula (5). 22.9 parts of the sodium salt were obtained as blue crystals. λmax: 629 nm (in an aqueous solution).
(2) Synthesis of copper phthalocyanine tetrasulfonic acid chloride (β-substituted type) (compound of formula (7) where M = Cu)
To 79 parts of chlorosulfonic acid, 9.8 parts of copper phthalocyanine tetrasulfonic acid tetrasodium salt was gradually added at 60 ° C. or lower while stirring, and the reaction was carried out at 120 ° C. for 4 hours. Next, the reaction solution was cooled to 80 ° C., 47.6 parts of thionyl chloride was added dropwise over 30 minutes, and the reaction was carried out at 80 ° C. for 2 hours and then at 90 ° C. for 1 hour. The reaction solution was cooled to 30 ° C. or lower, slowly poured into 700 parts of ice water, and the precipitated crystals were filtered, washed with 200 parts of an ice-cooled 2% aqueous hydrochloric acid solution, and wet cake of copper phthalocyanine tetrasulfonic acid chloride 35. Two parts were obtained.

(3) Synthesis of target compound (β-substituted product) 17.6 parts of the copper phthalocyanine tetrasulfonic acid chloride wet cake obtained in (2) was added to 100 parts of ice water and stirred and suspended. Ten minutes later, while maintaining the temperature at 5 ° C. or lower, 28% aqueous ammonia was added dropwise to adjust the pH to 9.0. Next, an aqueous solution in which 1.3 parts of taurine was dissolved in 50 parts of water was added to the suspension, and the pH was maintained at 9.0 while adding 28% aqueous ammonia. The reaction was performed for 2 hours at 50 ° C. for 1 hour. Water was added to adjust the liquid volume to 200 parts, and 30 parts of sodium chloride was added to precipitate crystals. The precipitated crystals were separated by filtration and washed with 100 parts of a 15% aqueous sodium chloride solution to obtain 44.3 parts of a wet cake. It was again dissolved in water, the total amount was adjusted to 200 parts, the temperature was raised to 60 ° C., 10 parts of sodium chloride was added, the pH was adjusted to 2 by adding a 35% hydrochloric acid aqueous solution, and crystals were precipitated. The precipitated crystals were separated by filtration and washed with 100 parts of a 5% aqueous sodium chloride solution. Thus, 31.8 parts of a wet cake of the compound represented by 1 was obtained.
31.8 parts of the obtained wet cake was put into 260 parts of methanol, 13 parts of water was added, and the mixture was stirred and suspended at 60 ° C. for 1 hour, filtered, washed with methanol, and dried to obtain blue crystals 4.3. Parts were obtained as
This dye had a β-substituted substance of 75% or more, a λmax in water of 603.0 nm, and a solubility of 10% (in water of pH 9.5). When estimated from the reaction and the charged amount of the raw materials, the compound is one in which m is 2 and n is 2 in the following formula (8) (substitution position is shown in the form of a free acid without being characterized). However, as a result of analysis with a liquid chromatograph mass spectrometer, a sulfonic acid group was also confirmed, and the value of l (sulfonic acid group) was about 0.3 and the value of n (substituted sulfamoyl group) ) Is estimated to be 0.3 to 2, so the remainder is m (unsubstituted sulfamoyl group), and the sum of l, m, and n is considered to be actually close to 4.

Example 2 (ink evaluation)
(A) Preparation of ink An ink was obtained by mixing and dissolving each component shown in Table 6 below and filtering through a 0.45 μm membrane filter (manufactured by Advantech). The water used was ion-exchanged water. Water and caustic soda (pH adjuster) were added so that the pH of the ink became pH 9 and the total amount became 100 parts. The ink using the compound of Example 1 was C-1.

Table 6
Compound obtained in Example 1 above 1.3 parts Water + 79.6 parts of caustic soda 5.0 parts of glycerin 5.0 parts of urea 5.0 parts of N-methyl-2-pyrrolidone 4.0 parts of IPA (isopropyl alcohol) 3.0 parts Butyl carbitol 2.0 parts Surfynol 104PG50 (trade name: Nissin Chemical Co., Ltd.) 0.1 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 Avesia: Comparative Example 1), and a method described in Example 1 of Patent Document 8 described above. The purified phthalocyanine dye (Comparative Example 2) was prepared in the same manner so that the printing density at the time of printing was the same as that of the ink of Example 1 in Table 6. The ink using the product of Comparative Example 1 was CA, and the ink using the compound of Comparative Example 2 was CB.

(B) Ink jet printing Using an ink jet printer (trade name: BJ S630, manufactured by Canon Inc.), dedicated paper A (HR-101S, high-grade exclusive paper manufactured by Canon Inc.), and exclusive paper B (hp premium inkjet exclusive paper, manufactured by Hewlett Packard Co., Ltd. Q1948A) 2) was subjected to inkjet recording.

(C) Evaluation of recorded image Hue Evaluation The hue of the recorded image is obtained by measuring the color of the recording paper using a color measurement system (GRETAG SPM50: manufactured by GRETAG), and determining the a ^* and b ^* values when the L ^{* of} the printed matter is in the range of 40 to 80. The color was measured. The evaluation was performed in three steps, defining a preferable a ^* value as −60 to −20 and a b ^* value as −60 to −20.
：: Both a ^* and b ^* values are present in a preferable region Δ: Only one of a ^* and b ^* values is present in a preferable region ×: Both a ^* and b ^* values are present outside a preferable region

2. The test piece of the image recorded in the light fastness test was irradiated with a xenon weather meter (Model: CI4000, manufactured by ATLAS) at an illuminance of 0.36 W / m 2 for 50 hours under the conditions of a tank temperature of 24 ° C. and a humidity of 60% RH. After the test, the reflection densities before and after the test were measured using a colorimetric system, with the reflection density (D value) in the range of 0.90 to 1.10. After the measurement, the dye residual ratio was calculated by (reflection density after test / reflection density before test) × 100 (%), and evaluated in three steps.
：: Residual rate 70% or more Δ: Residual rate 50 to 70%
×: Residual rate less than 50%

3. The test piece of the image recorded in the ozone resistance test was left for 3 hours at an ozone concentration of 12 ppm, a temperature in the tank 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 densities before and after the test were measured using the above-mentioned colorimetric system, with the reflection density (D value) in the range of 0.90 to 1.10. After the measurement, the dye residual ratio was calculated by (reflection density after test / reflection density before test) × 100 (%), and evaluated in three steps.
：: Residual rate 70% or more Δ: Residual rate 40 to 70%
×: Residual rate less than 40%

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

Table 7 (Exclusive Paper A) and Table 7 show the results of the hue evaluation, the light resistance test result, the ozone resistance test result, and the moisture resistance test result of the recorded image of the ink (C-1) using the compound obtained in Example 1, respectively. 8 (special paper B).

Table 7
Ink evaluation result: Special paper A
Ink number Hue Light resistance Ozone resistance Moisture resistance C-1 ○ ○ ○ ○
CA ○ ○ × ○
CB ○ ○ × ○

Table 8
Ink evaluation result: Special paper B
Ink number Hue Light resistance Ozone resistance Moisture resistance C-1 ○ ○ ○ ○
CA ○ ○ × ○
CB ○ ○ × ○

As is clear from Tables 7 and 8, the cyan ink using the compound of the present invention is excellent in hue, light resistance, ozone resistance and moisture resistance. In particular, it is clear that the ozone resistance is excellent.

Example 3 (ink set)
In an inkjet printer (BJ F850 manufactured by Canon Inc.) having a cyan ink set in which two types of densities of light cyan and dark cyan are set, C-1 is used as the light cyan ink, and Canon genuine is used as the dark cyan ink. With the cyan ink attached, ink jet recording was performed on two kinds of special paper A (high-quality special paper HR-101S manufactured by Canon Inc.) and special paper B (hp premium ink jet special paper Q1948A manufactured by Hewlett Packard). As for the printing result, clear dots were obtained without any missing dots or the like and satisfactory as a full-color image printing. As a result, it was confirmed that the ink of the present invention can be used for an inkjet printer having a cyan ink set in which two types of densities of light cyan and dark cyan are set.

The ink using the phthalocyanine dye of the present invention has a good hue as a cyan ink and is excellent in light fastness, ozone fastness and moisture fastness. Further, there is no crystal precipitation, physical property change, color change and the like after long-term storage, and the storage stability is good. Further, when used together with other magenta ink and yellow ink, it is possible to color tone in a wide visible region. Therefore, the cyan ink using the phthalocyanine dye of the present invention is extremely useful as an ink for inkjet recording.

Claims (20)

Phthalocyanine dye represented by formula (1) having at least one or more unsubstituted sulfamoyl groups and substituted sulfamoyl groups as substituents

ＭIn the formula (1), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide or a metal halide. R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ are each independently an unsubstituted sulfamoyl group represented by the formula (2), a substituted group represented by the formula (3) Represents a sulfamoyl group or a hydrogen atom. However, at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ is an unsubstituted sulfamoyl group, and at least one is a substituted sulfamoyl represented by the formula (3). Group. R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ each represent a hydrogen atom. The sum of the number of unsubstituted sulfamoyl groups and the number of substituted sulfamoyl groups is 2 to 4, the number of unsubstituted sulfamoyl groups is 1 to 3, and the number of substituted sulfamoyl groups is 1 to 3. ｝

In the formula (3), R ₁₇ and R ₁₈ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents an aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group, and R ₁₇ and R ₁₈ may be linked to each other to form a ring. However, the case where both R ₁₇ and R ₁₈ are hydrogen atoms is excluded. Further, at least one of R ₁₇ and R ₁₈ has an ionic hydrophilic group as a substituent. ｝ The phthalocyanine dye according to claim 1, wherein in the formula (1) according to claim 1, M is Cu.

(Wherein, R _{1 to} R ₁₆ have the same meaning as in formula (1)). In each combination of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R ₁₅ , one is a hydrogen atom and the other is an unsubstituted compound represented by the formula (2). A sulfamoyl group, a substituted sulfamoyl group represented by the formula (3) or a hydrogen atom, and at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ Is a substituted sulfamoyl group, and at least one is a substituted sulfamoyl group represented by the formula (3). R ₁₇ and R ₁₈ are each independently selected from the group consisting of a hydrogen atom, an alkyl group (sulfonic acid group, carboxyl group, hydroxyl group, alkoxy group, dialkylamino group, arylamino group, aryl group, halogen atom, cyano group Phenyl group (sulfonic acid group, carboxyl group, hydroxyl group, dialkylamino group, arylamino group, acetylamino group, ureido group, alkyl group, alkoxy group, nitro group, cyano group , A heterocyclic group, or a substituent selected from the group consisting of a halogen atom, a naphthyl group (may be substituted with a sulfonic acid group or a hydroxyl group), and a benzyl group. (May be substituted with a sulfonic acid group) and a phenethyl group (may be substituted with a sulfonic acid). Phthalocyanine dyes described in displacement or claim R ₁₇ is a hydrogen atom, a carboxy (C1-C5) alkyl group, a (C1-C5) alkyl group, a hydroxy (C1-C5) alkyl group, or a sulfo (C1-C5) alkyl group, and R ₁₈ is a sulfo (C1 -C5) alkyl group, carboxy (C1-C5) alkyl group, sulfonic acid group, phenyl group having a carboxyl group or hydroxyl group, di (sulfo (C1-C5) alkyl) amino (C1-C5) alkyl group, sulfonic acid group A benzotriazolyl group substituted by a phenyl group having a carboxyl group or a hydroxyl group, a phenyl group substituted by a benzotriazole group having a sulfonic acid group, a carboxyl group or a hydroxyl group, a naphthyl group having a sulfonic acid group or a hydroxyl group, sulfone Uracil group having acid group, carboxyl group or hydroxyl group, sulfonic group, carbo group Triazole group having a sil group or a hydroxyl group, sulfonic acid group, thiazolyl group having a carboxyl group or a hydroxyl group, sulfonic acid group, benzothiazolyl group having a carboxyl group or a hydroxyl group, sulfonic acid group, pyridine group having a carboxyl group or a hydroxyl group, sulfonic acid The phthalocyanine dye according to any one of claims 1 to 3, which is a benzimidazolyl group having a carboxyl group, a carboxyl group, or a hydroxyl group. 2. The phthalocyanine dye according to claim 1, wherein the content of the dye of the formula (1) is at least 60% or more based on the whole dye. Formula (1) is obtained by reacting a phthalocyanine dye represented by Formula (5) or a salt thereof with a chlorinating agent to convert a sulfonic acid group to a chlorosulfone group, and then reacting the amidating agent in the presence of an organic amine. The phthalocyanine dye according to any one of claims 1 to 5, which is obtained by the above method.

｛In the formula (5), M represents a hydrogen atom, a metal element, a metal oxide, or a metal halide, and L represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion or an ammonium ion of an organic amine, respectively. . a, b, c, and d are 0 or 1, and the sum thereof is an integer of 2 to 4. ｝ A chlorinating agent is allowed to react with a sulfometal phthalocyanine compound or a salt thereof obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a metal compound. Is converted to a chlorosulfone group and then reacted with an amidating agent and an organic amine to obtain a phthalocyanine dye. An ink comprising the phthalocyanine dye according to any one of claims 1 to 8 as a dye component. The ink according to claim 9, which contains an organic solvent. The ink according to claim 9 or 10, which is for inkjet recording. An ink set using two or more cyan inks having different dye concentrations, wherein at least one of the inks uses the ink according to any one of claims 9 to 11. 13. An ink jet recording method for recording on a recording material by discharging ink droplets according to a recording signal, wherein the ink according to claim 9 or the ink set according to claim 12 is used. Ink jet recording method characterized by the following 14. The ink jet recording method according to claim 13, wherein the recording material is an information transmission sheet. The ink jet recording method according to claim 14, wherein the information transmission sheet is a surface-treated sheet, and has an ink image receiving layer containing white inorganic pigment particles on a support. A container containing the ink or ink set according to any one of claims 9 to 12. An ink jet printer having the container according to claim 16. A colored body colored with the ink or the ink set according to any one of claims 9 to 12. A chlorinating agent is reacted with a compound obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a copper compound to react a chlorinating agent with A phthalocyanine dye obtained by reacting an amidating agent with an organic amine after conversion into a group The following equation (9)

中 In the formula, M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide or a metal halide, 1 is less than 1 including 0, m is 1 or more and 3.7 or less, and n is 0.1 or less. 3 or more and 3 or less, the sum of l, m and n is 2 or more and 4 or less, and R ₁₇ and R ₁₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclo group. Represents an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group, wherein R ₁₇ and R ₁₈ are linked to each other to form a ring; May be formed. However, the case where both R ₁₇ and R ₁₈ are hydrogen atoms is excluded. Further, at least one of R ₁₇ and R ₁₈ has an ionic hydrophilic group as a substituent. ｝
In the phthalocyanine dye represented by the formula, the β-substituted product is 60% or more and the α-substituted product is 40% or less.