JP5789503B2 - Phthalocyanine dye, coloring composition, inkjet ink, inkjet recording method, and phthalocyanine compound - Google Patents

Description

  The present invention relates to a phthalocyanine dye, a coloring composition containing a phthalocyanine dye, an inkjet ink, an inkjet recording method, and a phthalocyanine compound.

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. Further, a color filter is used for recording and reproducing a color image in an imaging device such as a CCD in a photographing apparatus and in an LCD or PDP in a display.

  In these color image recording materials and color filters, three primary colors (dyes and pigments) of so-called additive color mixing and subtractive color mixing are used to reproduce or record full color images. The fact is that there are no fast-acting dyes that have realizable absorption characteristics and can withstand various use conditions, and improvements are 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 of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force.

  As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.

  For dyes used in such inks for ink jet recording, the solvent has good solubility or dispersibility, high-density recording is possible, hue is good, light, heat, in the environment Fast against active gases (NOx, ozone and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image-receiving materials, and low bleeding. It is required that the ink has excellent storability, has no toxicity, has high purity, and can be obtained at low cost.

  However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, when printing on an image receiving material having an ink receiving layer that has a good cyan hue and is robust to light, humidity, and heat, especially containing porous white inorganic pigment particles, It is strongly desired to be robust against oxidizing gases such as ozone.

  Cyan dye skeletons used in such inks for ink jet recording include phthalocyanine, anthraquinone, and triphenylmethane, and phthalocyanine compounds with excellent hue and light fastness are used. In particular, since it does not have sufficient fastness to ozone and ink stability cannot be satisfied, improvement is desired.

  The phthalocyanine dye represented by Direct Blue 87 or Direct Blue 199, which is currently widely used, and also described in the above publications, etc., has a feature that it is superior in light resistance compared to magenta and yellow, but is soluble in dye. In many cases, for example, a dissolution failure occurs at the time of manufacturing, resulting in a manufacturing trouble, or an insoluble material precipitates during product storage or use. In particular, the above-described ink jet recording has problems such as clogging of the print head and ejection failure due to poor ink storage stability such as precipitation of dye, leading to significant deterioration of the printed image.

  Moreover, it is easy to fade with oxidizing gases such as ozone, which are often cited as environmental problems, and the print density is greatly reduced.

  Currently, inkjet recording is rapidly expanding in the field of use, and as it becomes increasingly widely used in general households, SOHO, business fields, etc., it will be exposed to various usage conditions and environments, resulting in the dissolution of cyan dye. There are many cases where troubles in ink storage stability due to inferiority of the ink occur or exposure to light or an active gas in the environment causes a problem of fading of the printed image. Accordingly, a dye and ink composition having particularly good hue, excellent light fastness and fastness in active gases in the environment (oxidizing gases such as NOx, ozone, etc., SOx, etc.) and high solubility are provided. It is increasingly strongly desired.

As described above, the characteristics of the ink, particularly the ink used in the ink jet recording method, largely depend on the characteristics unique to the dye, and the selection of the dye is extremely important. As a dye for improving the above problem, recently, in Patent Document 1, at least one of the 2nd, 3rd, 6th, 7th, 10th, 11th, 14th and 15th positions is -SO-Z or A phthalocyanine compound substituted with —SO ₂ —Z (Z: substituted or unsubstituted alkyl group or the like) is disclosed. In Patent Document 2, a chlorine atom and an alkylsulfonyl group are substituted on the 2-position, 3-position, 6-position, 7-position, 10-position, 11-position, 14-position and 15-position of the phthalocyanine ring, respectively. Phthalocyanine compounds are disclosed. Patent Document 3 discloses a phthalocyanine compound (Pigment Green 7 or the like) in which 15 to 16 positions out of 1 to 16 positions are substituted with chlorine atoms. Patent Document 4 discloses a phthalocyanine compound in which a chlorine atom is substituted at the 2-position, 3-position, 10-position and 11-position of the phthalocyanine ring and an alkylsulfonyl group is substituted at the 5-position, 8-position, 13-position or 16-position. ing.
In any of Patent Documents 1 to 3, the specific phthalocyanine structure improves ozone fastness, light fastness, water fastness and other image fastnesses and storage stability, and contributes to improved performance as an inkjet ink. doing. Patent Document 4 contributes to the provision of a photothermographic material capable of obtaining an image free from unevenness in bluish density in an image by a specific phthalocyanine structure.

Japanese Patent Laid-Open No. 2002-249677 JP-A-2005-075778 JP 2009-173853 A JP 2007-065000 A

  However, the dyes described in Patent Documents 1 to 3 have no description about improvement in print density and water solubility, and there is room for further study. The coloring matter described in Patent Document 3 is a pigment and is not suitable for use as a dye that requires water solubility. The dye described in Patent Document 4 is for use as a photothermographic material, and there is no description about use in ink-jet ink.

  As a result of intensive studies in view of the above-mentioned circumstances, the present inventors have found that a dye having a substituted sulfonyl group and a halogen atom introduced at a specific position of phthalocyanine is excellent in maintaining image fastness such as ozone resistance. It has been found that an image having a hue and free from bronzing can be formed, and a high printing density and water solubility can be realized, and the present invention has been completed.

（一般式（１）中、環Ａ〜Ｄのうちの３つが一般式（２）又は一般式（３）で表される環であり、環Ａ〜Ｄのうちの１つが一般式（４）で表される環である。
Ｚ ^１ 及びＺ ^２ は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。複数のＺ ^１ 及びＺ ^２ は同じであっても異なっていてもよい。
Ｘ ^１ 〜Ｘ ^４ は、それぞれ独立に、水素原子又はハロゲン原子を表す。
但し、Ｘ ^１ 〜Ｘ ^４ の少なくとも１つは、ハロゲン原子である。
＊はフタロシアニン環の結合位置を表す。
一般式（１）で表されるフタロシアニン染料は、少なくとも１つはスルホ基、カルボキシル基、チオカルボキシル基、スルフィノ基、ホスホノ基、ジヒドロキシホスフィノ基、及び４級アンモニウム基より選択されるイオン性親水性基を置換基として有する。）
＜２＞
前記環Ａ〜Ｄのうちの３つが一般式（２）で表される環であり、環Ａ〜Ｄのうちの１つが一般式（４）で表される環であることを特徴とする、＜１＞に記載のフタロシアニン染料。
＜３＞
前記Ｘ ^１ 〜Ｘ ^４ のうちの２つがハロゲン原子であることを特徴とする、＜１＞又は＜２＞に記載のフタロシアニン染料。
＜４＞
前記Ｘ ^１ 及びＸ ^４ が水素原子であり、Ｘ ^２ 及びＸ ^３ がハロゲン原子であることを特徴とする、＜３＞に記載のフタロシアニン染料。
＜５＞
前記イオン性親水性基がスルホ基であることを特徴とする、＜１＞〜＜４＞のいずれか一項に記載のフタロシアニン染料。
＜６＞
＜１＞〜＜５＞のいずれか一項に記載のフタロシアニン染料を含有する着色組成物。
＜７＞
＜６＞に記載の着色組成物を含有するインクジェット用インク。
＜８＞
＜６＞に記載の着色組成物又は＜７＞に記載のインクジェット用インクを用いて、画像形成することを特徴とするインクジェット記録方法。
＜９＞
一般式（１）で表されるフタロシアニン化合物。

（一般式（１）中、環Ａ〜Ｄのうちの３つが一般式（２）又は一般式（３）で表される環であり、環Ａ〜Ｄのうちの１つが一般式（４）で表される環である。
Ｚ ^１ 及びＺ ^２ は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。複数のＺ ^１ 及びＺ ^２ は同じであっても異なっていてもよい。
Ｘ ^１ 〜Ｘ ^４ は、それぞれ独立に、水素原子又はハロゲン原子を表す。
但し、Ｘ ^１ 〜Ｘ ^４ の少なくとも１つは、ハロゲン原子である。
＊はフタロシアニン環の結合位置を表す。
一般式（１）で表されるフタロシアニン化合物は、少なくとも１つはスルホ基、カルボキシル基、チオカルボキシル基、スルフィノ基、ホスホノ基、ジヒドロキシホスフィノ基、及び４級アンモニウム基より選択されるイオン性親水性基を置換基として有する。）
本発明は、前記＜１＞〜＜９＞に係る発明であるが、以下、それ以外の事項についても参考のため記載している。
〔１〕
一般式（１）で表されるフタロシアニン染料。 That is, the present invention is as follows.
<1>
A phthalocyanine dye represented by the general formula (1).

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
At least one phthalocyanine dye represented by the general formula (1) is an ionic hydrophilic group selected from a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Having a functional group as a substituent. )
<2>
Three of the rings A to D are rings represented by the general formula (2), and one of the rings A to D is a ring represented by the general formula (4), The phthalocyanine dye as described in <1>.
<3>
The phthalocyanine dye according to <1> or <2>, wherein two of X ^{1 to} X ⁴ are halogen atoms.
<4>
The phthalocyanine dye according to <3>, wherein X ¹ and X ⁴ are hydrogen atoms, and X ² and X ³ are halogen atoms.
<5>
The phthalocyanine dye according to any one of <1> to <4>, wherein the ionic hydrophilic group is a sulfo group.
<6>
The coloring composition containing the phthalocyanine dye as described in any one of <1>-<5>.
<7>
An ink-jet ink containing the colored composition according to <6>.
<8>
An inkjet recording method comprising forming an image using the colored composition according to <6> or the inkjet ink according to <7>.
<9>
A phthalocyanine compound represented by the general formula (1).

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
The phthalocyanine compound represented by the general formula (1) has at least one ionic hydrophilic group selected from a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Having a functional group as a substituent. )
The present invention is an invention according to the above <1> to <9>, but hereinafter, other matters are also described for reference.
[1]
A phthalocyanine dye represented by the general formula (1).

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
At least one of the phthalocyanine dyes represented by the general formula (1) has an ionic hydrophilic group as a substituent. )
[2]
Three of the rings A to D are rings represented by the general formula (2), and one of the rings A to D is a ring represented by the general formula (4), The phthalocyanine dye according to [1] above.
[3]
The phthalocyanine dye according to [1] or [2] above, wherein two of the X ^{1 to} X ⁴ are halogen atoms.
[4]
The phthalocyanine dye as described in [3] above, wherein X ¹ and X ⁴ are hydrogen atoms, and X ² and X ³ are halogen atoms.
[5]
The phthalocyanine dye according to any one of the above [1] to [4], wherein the ionic hydrophilic group is a sulfo group.
[6]
The coloring composition containing the phthalocyanine dye as described in any one of said [1]-[5].
[7]
An inkjet ink containing the colored composition according to the above [6].
[8]
An ink jet recording method comprising forming an image using the colored composition according to the above [6] or the ink jet ink according to the above [7].
[9]
A phthalocyanine compound represented by the general formula (1).

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
At least one of the phthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. )

  According to the present invention, it is possible to form an image having a good hue and having no bronzing phenomenon while maintaining image fastness including ozone resistance, and a specific position capable of realizing a high print density. There are provided a phthalocyanine compound having a substituted sulfonyl group and a halogen atom introduced therein, a phthalocyanine dye, a coloring composition containing the dye, an inkjet ink, and an inkjet recording method.

  A phthalocyanine dye represented by the general formula (1).

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
At least one of the phthalocyanine dyes represented by the general formula (1) has an ionic hydrophilic group as a substituent. )

  Hereinafter, the present invention will be described in detail.

  In the present invention, when the compound is a salt, the salt is dissociated into ions in the ink, but is expressed as “contains a salt” for convenience.

Hereinafter, the phthalocyanine dye (compound) represented by the general formula (1) of the present invention will be described in detail.
[Phthalocyanine dye represented by formula (1)]
The phthalocyanine dye represented by the general formula (1) of the present invention includes a dye, a salt thereof, and a hydrate thereof.
The phthalocyanine dye of the present invention is a phthalocyanine dye represented by the general formula (1). As the rings A to D, a ring represented by the three general formulas (2) or (3) and one general And a ring represented by the formula (4).
The phthalocyanine dye of the present invention is substituted by the ring represented by the general formula (4) and the electron withdrawing ability of the sulfonyl group substituted on the ring represented by the general formula (2) or (3). In addition, due to the electron-withdrawing ability and the association-promoting effect by halogen atoms, image fastness such as ozone resistance can be maintained. Furthermore, it has favorable hue by making cyan absorption with less redness by lengthening visible absorption by the halogen substituted on the ring represented by the general formula (4). Moreover, water solubility is high with the sulfo group introduce | transduced into the ring represented by General formula (2) or General formula (3). Particularly, those having a ring represented by the general formula (2) can form an image in which no bronzing phenomenon occurs by suppressing the association due to the steric hindrance. Having the ring A to D in a ratio of three rings represented by the general formula (2) or the general formula (3) and one ring represented by the general formula (4) It is important from a viewpoint. Further, since the printing density on plain paper is high and a clear cyan color is exhibited, it is useful as an inkjet ink.

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
At least one of the phthalocyanine dyes represented by the general formula (1) has an ionic hydrophilic group as a substituent. )

  In the phthalocyanine dye represented by the general formula (1), phthalocyanine derivatives having different substitution positions are classified and defined as the following three types. Hereinafter, when the phthalocyanine derivatives having different substitution positions are described, the following (a) α- Position substitution type, (b) β-position substitution type, (c) α, β-position mixed substitution type.

  (A) α-position substitution type: Of the rings A to D in the general formula (1), any ring other than the ring represented by the general formula (4) is represented by the general formula (2). When representing a ring.

  (B) β-position substitution type: Of the rings A to D in the general formula (1), any ring other than the ring represented by the general formula (4) is represented by the general formula (3). When representing a ring.

  (C) α, β-position mixed substitution type: Of the rings A to D in the general formula (1), a ring other than the ring represented by the general formula (4) is represented by the general formula (2). When both the ring and the ring represented by formula (3) are included.

In general formulas (2) and (3), Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted It represents a substituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.

Examples of the alkyl group for Z ¹ and Z ² include linear and branched alkyl groups.
As the alkyl group, an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, 2- A chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group and the like can be mentioned.

Examples of the cycloalkyl group of Z ¹ and Z ² include a cycloalkyl group, a bicycloalkyl group, and a tricyclo structure having many ring structures.
Preferred examples of the cycloalkyl group include substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, such as a cyclohexyl group, a cyclopentyl group, and 4-n-dodecylcyclohexyl group. As the bicycloalkyl group, Preferably, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] Examples include a heptan-2-yl group and a bicyclo [2,2,2] octane-3-yl group.

Examples of the alkenyl group for Z ¹ and Z ² include linear and branched alkenyl groups.
Preferred examples of the alkenyl group include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms such as vinyl group, allyl group, prenyl group, geranyl group, and oleyl group.

As the aralkyl group of Z ¹ and Z ^2, an aralkyl group having 7 to 30 carbon atoms is preferable. For example, a benzyl group and a 2-phenethyl group can be mentioned.

The aryl group for Z ¹ and Z ² is preferably an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like. Is mentioned.

The heterocyclic group for Z ¹ and Z ² is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, more preferably carbon. Examples thereof include 5- or 6-membered aromatic heterocyclic groups of 3 to 30, for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like.
The heterocyclic group of Z ¹ and Z ² is preferably bonded to the SO ₂ group of —SO ₂ Z ¹ or —SO ₂ Z ² through a carbon atom in the heterocyclic group.

Examples of the substituent that Z ¹ and Z ² may have include the following substituent group A.
(Substituent group A)
For example, halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group , Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group , Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarboni Group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, ionic hydrophilic group (for example, carboxyl group) , Sulfo groups, and quaternary ammonium groups). These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

  More specifically, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group. Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl. Group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group and the like, and the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group, A cyclopentyl group, 4-n-dodecylcyclohexyl group and the like. The bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups from which one hydrogen atom has been removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicycl [2,2,2] octan-3-yl group.

  Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenethyl group can be mentioned.

  Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups. Specifically, the alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, and the like. Is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopentene-1 -Yl group, 2-cyclohexen-1-yl group and the like, and as the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, That is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond, for example, bicyclo [2 2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like. Can be mentioned.

  The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a carbon number. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

  The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group. Etc.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group etc. are mentioned.

  Preferred examples of the silyloxy group include substituted or unsubstituted silyloxy groups having 0 to 20 carbon atoms such as a trimethylsilyloxy group and a diphenylmethylsilyloxy group.

  Preferred examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as an acetyloxy group, Examples include a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.

  The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group. Etc.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples include phenoxycarbonyloxy group.

  The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms. Examples of the substituted anilino group include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and a triazinylamino group.

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as an acetylamino group, Examples include pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, N, N-dimethylaminocarbonylamino group, or N, N-diethylaminocarbonylamino group. And a morpholinocarbonylamino group.

  The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino. Group, N-methyl-methoxycarbonylamino group and the like.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn- Examples include octylaminosulfonylamino group.

The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.
Preferred examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.

  Preferred examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

  Preferred examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms, such as a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfuryl group. Examples include a famoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, and an N- (N′-phenylcarbamoyl) sulfamoyl group.

  The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, phenyl. Examples thereof include a sulfinyl group and a p-methylphenylsulfinyl group.

  The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, or a phenyl group. A sulfonyl group, p-methylphenylsulfonyl group, etc. are mentioned.

  The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt- A butylphenoxycarbonyl group etc. are mentioned.

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.

  The aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo and the like.

  Preferred examples of the imide group include an N-succinimide group and an N-phthalimide group.

  The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, and the like.

  The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

  Preferred examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 0 to 30 carbon atoms such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.

  Preferred examples of the silyl group include substituted or unsubstituted silyl groups having 0 to 30 carbon atoms such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

In general formula (1), three of rings A to D are rings represented by general formula (2) or general formula (3), and one of rings A to D is general formula (4). The ring represented.
From the viewpoint of achieving high printing density by suppressing dye association, three of the rings A to D are rings represented by the general formula (2), and one of the rings A to D is represented by the general formula ( The ring represented by 4) is preferable. That is, among the rings A to D, any of the rings other than the ring represented by the general formula (4) is preferably a ring represented by the general formula (2).

In General Formula (4), X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.

X ^{1 to} X ⁴ are each independently a hydrogen atom or a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
As the halogen atom, a chlorine atom is preferable.

At least one of X ^{1 to} X ⁴ is a halogen atom, and preferably 2 to ⁴ of X ^{1 to} X ⁴ are halogen atoms. From the viewpoint of hue, two of X ^{1 to} X ⁴ are halogens. More preferably, it is an atom.

When two of X ^{1 to} X ⁴ are halogen atoms, X ¹ and X ⁴ , or X ² and X ³ are preferably halogen atoms. From the viewpoint of availability of raw materials, X ² and X ³ Is more preferably a halogen atom.

  At least one of the phthalocyanine dyes represented by the general formula (1) has an ionic hydrophilic group as a substituent. As the number of ionic hydrophilic groups, those having at least 2 in one molecule of phthalocyanine compound are preferable, those having at least 2 to 8 ionic hydrophilic groups selected from a sulfo group and a carboxyl group are more preferable. Those having ˜4 are particularly preferred.

(Ionic hydrophilic group)
A sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, a quaternary ammonium group and the like can be mentioned. A sulfo group and a carboxyl group are preferable, and a sulfo group is particularly preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) is included, lithium salt, sodium salt, potassium salt, ammonium salt is preferable, lithium salt or mixed salt containing lithium salt as a main component Are more preferred, and lithium salts are most preferred.

[Phthalocyanine compound represented by general formula (1)]
The phthalocyanine compound represented by the general formula (1) of the present invention is the same as the range of the phthalocyanine dye represented by the general formula (1). What was used with the phthalocyanine dye represented by the said General formula (1) can also be used for the preferable form of the compound represented by General formula (1), a preferable substituent, and a synthesis method as it is.

  Specific examples of the phthalocyanine dye and the compound of the present invention represented by the general formula (1) are given below, but the present invention is not limited to these specific examples.

The phthalocyanine dyes and compounds of the present invention are difficult to produce by conventional synthesis methods. The method for synthesizing the phthalocyanine dye and compound of the present invention uses the phthalonitrile method.
However, the structure of the rings A to D in the general formula (1) includes three rings represented by the general formula (2) or the general formula (3) and one ring represented by the general formula (4). In order to control the reaction, the reaction is carried out using a completely dissolved reaction system. As a result, the dyes and compounds in which the configurations of the rings A to D are controlled as described above can be obtained as almost a single product with respect to the dyes and compounds in which the rings A to D are other configurations. Specific examples are illustrated in the examples.

(Coloring composition)
The coloring composition of the present invention contains at least one phthalocyanine dye of the present invention. The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The coloring composition of the present invention can be prepared by dissolving and / or dispersing the phthalocyanine dye of the present invention in a lipophilic medium or an aqueous medium as a medium. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium.

  In the present invention, the content of the phthalocyanine dye contained in the colored composition is determined by the type of substituent in the general formula (1) used, the type of solvent component used for producing the colored composition, and the like. The content of the phthalocyanine dye represented by the general formula (1) in the coloring composition or a salt thereof is preferably 1 to 10% by mass with respect to the total mass of the coloring composition, and 2 to 6% by mass. More preferably it is included.

  By making the content of the phthalocyanine dye represented by the general formula (1) contained in the coloring composition 1% by mass or more, the color development property of the ink on the recording medium when printing can be improved and necessary The image density can be ensured. Moreover, when the total amount of the phthalocyanine dye represented by the general formula (1) contained in the colored composition is 10% by mass or less, the discharge property of the colored composition is improved when used in the ink jet recording method. In addition, the ink jet nozzles are less likely to be clogged.

  The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include additives that can be used in ink jet recording inks described later.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The ink for inkjet recording can be produced by dissolving and / or dispersing the phthalocyanine dye (mixture) in an oleophilic medium or an aqueous medium. Preferably, the ink uses an aqueous medium.
If necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.

  As the anti-drying agent, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration enhancer is preferably used for the purpose of allowing the ink for inkjet to penetrate better into paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants and the like can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, U.S. Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21114, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading 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. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, the neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjuster is preferably added to summer for pH 6 to 10 and more preferably pH 7 to 10 for summer. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m. Furthermore, 25-60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the phthalocyanine dye of the present invention is dispersed in an aqueous medium, as described in JP-A-11-286637, Japanese Patent Application Nos. 2000-78491, 2000-80259, 2000-62370, and the like. In addition, dispersed fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium, or in each specification of Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, 2000-203857. Thus, it is preferable to disperse the phthalocyanine dye of the present invention dissolved in a high boiling point organic solvent in an aqueous medium. The specific method for dispersing the phthalocyanine dye of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount used thereof are preferably those described in the above-mentioned patent publications, etc. can do. Alternatively, the phthalocyanine dye may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

  In 100 parts by mass of the inkjet recording ink of the present invention, the phthalocyanine dye is preferably contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less. Further, in the inkjet ink of the present invention, other pigments may be used in combination with the phthalocyanine dye. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The ink for inkjet recording of the present invention preferably has a viscosity of 30 mPa · s or less. The surface tension is preferably 25 mN / m or more and 70 mN / m or less. Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

  The ink for inkjet recording 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, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Any yellow dye 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); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

  Any applicable magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.

  Any applicable cyan dye can be used. For example, aryl or hetaryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Examples include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

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

[Inkjet recording method]
In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic paper, cloth, glass, metal, ceramics, etc. To do.

  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 of applying the polymer latex to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition place may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952, 2000-299465, 2000-297365, etc. The method described in the specification can be preferably used.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described.
The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or 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 backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used as the support.
It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and 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 pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. 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 resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,2,387,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 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 antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferred.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably 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, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat 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. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-resistant agent.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

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

  EXAMPLES Hereinafter, although the synthesis method of the phthalocyanine compound (mixture) of this invention is demonstrated in detail to an Example, this invention is not limited to these Examples at all.

  The typical phthalocyanine compound (mixture) of the present invention can be derived from, for example, the following synthetic route.

<Synthesis of Exemplary Compound (1A)>

  In a 1000 mL three-necked flask, 134 g of diethylene glycol (manufactured by Fischer), 21.2 g of ethyl orthoacetate (manufactured by Fischer), 0.63 g of acetic acid (manufactured by Fischer), 5.63 g of tetrachlorophthalonitrile (manufactured by Sigma Aldrich), 3- (2 , 3-dicyanobenzene-1-ylsulfonyl) sodium propanesulfonate (synthesized by the method described in WO2007 / 37039A1, page 67), heated and stirred at 100 ° C., then, anhydrous copper chloride 3. 0 g (manufactured by Fischer) and 24.8 g of ammonium benzoate (manufactured by Acros) were added and reacted at 100 ° C. for 24 hours. Concentrated hydrochloric acid 40mL was added to the reaction liquid, it cooled to 85 degreeC, acetone 360mL was dripped there, and the crystal | crystallization was deposited. After cooling to room temperature, the crystals were filtered off and washed thoroughly with acetone. The crystals separated by filtration are dissolved in 1000 mL of water, and after passing through a cation exchange resin (Amberlite IR-120Na, manufactured by Organo), desalting is performed using a dialysis tube until the electric conductivity becomes 10 μS, Dust removal was performed with a microfilter having an average pore diameter of 0.2 μm, and drying was performed in an oven at 60 ° C. to obtain 21.8 g of green glossy crystals of Exemplified Compound 1A. The absorption maximum wavelength in the diluted aqueous solution was 659.5 nm.

<Synthesis of Exemplary Compound (1B)>
In the synthesis method of the exemplary compound (1A), synthesis was performed in the same manner except that tetrachlorophthalonitrile was changed to 4.14 g of 4,5-dichlorophthalonitonyl. Yield 19.7 g. The absorption maximum wavelengths in the diluted aqueous solution were 617.5 nm and 658.0 nm.

[Example 1]
Deionized water was added to the following components to make 100 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L and filtered under reduced pressure through a microfilter having an average pore size of 0.25 μm to prepare cyan ink liquid A.

Composition of ink liquid A:
5.0 g of phthalocyanine dye of the present invention (Exemplary Compound 1)
Diethylene glycol 10.65g
Glycerin 14.70g
Diethylene glycol monobutyl ether 12.70g
Triethanolamine 0.65g
Olfin E 1010 0.9g

[Examples 2-3 and Comparative Examples 1-4]
Ink liquids D to G were prepared using the following compounds as ink liquids B to C and comparative ink liquids in the same manner as ink liquid A, except that the dyes were changed as shown in the following table. did.

(Image recording and evaluation)
The following evaluation was performed on the ink jet inks of the above Examples (Ink Liquids A to C) and Comparative Examples (Ink Liquids D to G). The results are shown in Table 1.
In Table 1, the ozone resistance, hue, and bronze evaluation are based on photo glossy paper (PMSON paper manufactured by EPSON <gloss>) using an inkjet printer (manufactured by EPSON Corporation; PM-700C). (KA420PSK, EPSON) After the image was recorded, the print density was determined by using each inkjet recording ink with an inkjet printer (manufactured by EPSON); The evaluation was made after recording an image on paper (GF500, Canon).

<Ozone resistance>
While passing dry air through the double glass tube of the Siemens type ozonizer, an AC voltage of 5 kV was applied, and using this, the ozone gas concentration was 0.5 ± 0.1 ppm, the room temperature was set in a dark place, The photo glossy paper on which the image was formed was allowed to stand for 14 days, and the image density before and after being left under ozone gas was measured using a reflection densitometer (X-Rite 310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.

<Print density>
The print density at a print density of 100% is measured using a reflection densitometer (X-Rite 310TR). The print density is 1.05 or more, A is 0.95 or more and less than 1.05, B is 0. The case of less than 95 was defined as C and evaluated in three stages.

<Hue>
The hue is visually evaluated in three stages: best, good and bad, A is the best hue; B is good, and C is bad.

<Bronze evaluation>
About the inkjet ink of each of the above Examples (Ink Liquids A to C) and Comparative Examples (Ink Liquids D to G), 1.5 to 2.2 mg per square inch on an inkjet dedicated recording medium (photo glossy paper). Cyan and Blue (Cyan + Magenta) were printed in a solid amount so as to achieve a driving amount of 5 mm, and the obtained printed matter was measured using a gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.) (measurement angle 60). Degree) and glossiness. Printing was evaluated in an environment of 25 ° C. and 50% RH. Using the obtained glossiness and the increased value calculated based on the following formula as a criterion for determining the degree of occurrence of bronze phenomenon, the determination was made based on the following criterion.
Increase value = Glossiness (printed material)-Glossiness (recording medium)
[Criteria]
Evaluation A: Less than 15 Evaluation B: 15 or more and less than 35 Evaluation C: 35 or more and less than 55 Evaluation D: 55 or more

  As is apparent from the results in Table 1, the inks of the examples using the dyes of the present invention have extremely high levels of ozone resistance, hue, suppression of bronze phenomenon, and print density compared to the other comparative examples. You can see that both are compatible.

Claims (9)

A phthalocyanine dye represented by the general formula (1).

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
At least one phthalocyanine dye represented by the general formula (1) is an ionic hydrophilic group selected from a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Having a functional group as a substituent. )   Three of the rings A to D are rings represented by the general formula (2), and one of the rings A to D is a ring represented by the general formula (4), The phthalocyanine dye according to claim 1. The phthalocyanine dye according to claim 1 or 2, wherein two of the X ^{1 to} X ⁴ are halogen atoms. Wherein X ¹ and X ⁴ are hydrogen atoms, characterized in that X ² and X ³ is a halogen atom, a phthalocyanine dye of claim 3.   The phthalocyanine dye according to claim 1, wherein the ionic hydrophilic group is a sulfo group.   The coloring composition containing the phthalocyanine dye as described in any one of Claims 1-5.   An ink-jet ink comprising the coloring composition according to claim 6.   An ink jet recording method comprising forming an image using the colored composition according to claim 6 or the ink jet ink according to claim 7. A phthalocyanine compound represented by the general formula (1).

(In General Formula (1), three of Rings A to D are rings represented by General Formula (2) or General Formula (3), and one of Rings A to D is General Formula (4). Is a ring represented by
Z ¹ and Z ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Represents a group or a substituted or unsubstituted heterocyclic group. The plurality of Z ¹ and Z ² may be the same or different.
X ^{1 to} X ⁴ each independently represent a hydrogen atom or a halogen atom.
However, at least one of X ^{1 to} X ⁴ is a halogen atom.
* Represents the bonding position of the phthalocyanine ring.
The phthalocyanine compound represented by the general formula (1) has at least one ionic hydrophilic group selected from a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Having a functional group as a substituent. )