JP5826004B2 - Coloring composition and ink jet recording ink - Google Patents

Description

  The present invention relates to a coloring composition and an ink jet recording ink which have good fastness and high printing density and are excellent in storage stability over time.

  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 a good cyan hue and being robust against light, humidity, and heat, especially an ink receiving layer containing porous white inorganic pigment particles, It is strongly desired to be robust against an oxidizing gas such as ozone therein, and at the same time, it is strongly desired to achieve both ink storage stability as described later.

  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.

  Further, it is a big problem that the printing density is greatly reduced due to the fading easily by an oxidizing gas such as ozone, which is often taken up as an environmental problem in recent years.

  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. Therefore, a dye and an ink composition having particularly good hue, excellent light fastness, fastness in the active gas in the environment (oxidizing gas such as NOx, ozone, etc., SOx), and high solubility are provided. It is increasingly strongly desired.

  A phthalocyanine dye having a specific sulfonyl group or sulfinyl group is described in Prior Document 1 as a phthalocyanine dye that achieves both hue, light and ozone fastness, and a phthalocyanine dye having a sulfo group and a substituted sulfamoyl group is described in Prior Document 2. Has been.

Japanese Patent Laid-Open No. 2002-249677 International Publication No. 2010/020802 Pamphlet

However, among the phthalocyanine dyes described in the prior art document 1, in the α, β-position mixed type, the ozone fastness and the print density are not sufficiently compatible. In the α, β-position mixed type as described above, the substitution position ratio {α position (positions 1, 4, 5, 8, 9, 12, 13 and 16) to β position (2, 3, 6, 7, 10), 11th, 14th, and 15th positions} are adjusted in the molecule to control the association, thereby balancing the print density and the robustness. That is, both are in a trade-off relationship, and the other performance was not sufficient to satisfy one performance.
In addition, the phthalocyanine dye described in the prior art document 1 is not sufficiently compatible with ozone fastness and printing density, and it has been found that there is room for further improvement in printing density.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a coloring composition and ink jet recording ink that suppresses bronze gloss and has good ozone gas fastness and high printing density.

  The present inventors have found that by using a mixture of a phthalocyanine having a specific structure and a phthalocyanine having a specific substituent, the association can be suppressed and the trade-off relationship can be avoided, and the present invention has been completed. . Moreover, it turned out that the coloring composition of this invention is excellent in the storage stability with time of being hard to precipitate also in high concentration aqueous solution unexpectedly. Excellent storage stability over time is advantageous in terms of storage and transportation because the aqueous dye solution used as an ink-jet ink raw material can be adjusted at a high concentration, and when preparing ink-jet ink using a high-concentration dye aqueous solution. In addition, since there is no precipitation of dyes and the like, it is difficult to cause a deviation in density, which is useful.

（一般式（１）中、
Ｒ _２ 、Ｒ _３ 、Ｒ _６ 、Ｒ _７ 、Ｒ _１０ 、Ｒ _１１ 、Ｒ _１４ 及びＲ _１５ は、水素原子を表す。
Ｚ _１ 、Ｚ _２ 、Ｚ _３ 、及びＺ _４ は、それぞれ独立に、置換若しくは無置換のアルキル基を表す。但し、Ｚ _１ 、Ｚ _２ 、Ｚ _３ 、及びＺ _４ のうち少なくとも１つは、スルホ基を置換基として有する。
ｌ、ｍ、ｎ、及びｐは１を表し、ｑ _１ 、ｑ _２ 、ｑ _３ 及びｑ _４ は２を表す。
Ｍ _１ は、Ｃｕを表す。）

（一般式（２）中、
Ｒ _１７ 及びＲ _１８ は水素原子を表す。
Ａはアルキレン基をそれぞれ表す。
Ｙ及びＺは、それぞれ独立してアミノ基、置換若しくは無置換のアルキルアミノ基、又は置換若しくは無置換のアリールアミノ基を表す。但し、Ｙ、Ｚのうち少なくとも１つは、スルホ基を置換基として有する基である。ｍ、及びｎは１から３であり、且つｍとｎの和は２から４である。）
＜２＞
前記一般式（２）で表されるフタロシアニン染料が、一般式（２−１）で表されるフタロシアニン染料である＜１＞に記載の着色組成物。

（一般式（２−１）中、
Ｒ ^２７ 及びＲ ^２８ は水素原子を表す。
Ａはアルキレン基をそれぞれ表す。
Ｒ ^２９ 、Ｒ ^２１０ 、及びＲ ^２１１ はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、Ｒ ^２１２ は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、スルホ基を少なくとも一つ置換基として有する。
ｍ、及びｎは１から３であり、且つｍとｎの和は２から４である。）
＜３＞
一般式（１）で表されるフタロシアニン染料と、一般式（２）で表されるフタロシアニン染料との質量比が５０／５０〜１０／９０である＜１＞又は＜２＞に記載の着色組成物。
＜４＞
一般式（１）で表されるフタロシアニン染料の含有量が１〜２０質量％である＜１＞〜＜３＞のいずれか１項に記載の着色組成物。
＜５＞
＜１＞〜＜４＞のいずれか１項に記載の着色組成物を含むインクジェット記録用インク。
本発明は、前記＜１＞〜＜５＞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。 The object of the present invention has been achieved by the following method.
<1>
A coloring composition comprising a phthalocyanine dye represented by the following general formula (1) and a phthalocyanine dye represented by the following general formula (2).

(In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ represent a hydrogen atom.
Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent a substituted or unsubstituted alkyl group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has a sulfo group as a substituent.
l, m, n, and p represent ₁ , and q ₁ , q ₂ , q _3, and q ₄ represent 2.
M ₁ represents Cu. )

(In general formula (2),
R ₁₇ and R ₁₈ represent a hydrogen atom.
A represents an alkylene group.
Y and Z each independently represent an amino group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group. However, at least one of Y and Z is a group having a sulfo group as a substituent. m and n are 1 to 3, and the sum of m and n is 2 to 4. )
<2>
The coloring composition as described in <1> whose phthalocyanine dye represented by the said General formula (2) is a phthalocyanine dye represented by General formula (2-1).

(In general formula (2-1),
R ²⁷ and ^{R 28} represents a hydrogen atom.
A represents an alkylene group.
R ²⁹ , R ²¹⁰ , and R ²¹¹ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ²¹² represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group. Represents a cyclic group and has at least one sulfo group as a substituent.
m and n are 1 to 3, and the sum of m and n is 2 to 4. )
<3>
The coloring composition as described in <1> or <2> whose mass ratio of the phthalocyanine dye represented by General formula (1) and the phthalocyanine dye represented by General formula (2) is 50 / 50-10 / 90 object.
<4>
The coloring composition according to any one of <1> to <3>, wherein the content of the phthalocyanine dye represented by the general formula (1) is 1 to 20% by mass.
<5>
<1>-<4> The inkjet recording ink containing the coloring composition of any one of <4>.
The present invention is the invention according to the above <1> to <5>, but other matters are described below for reference.

（一般式（１）中、
Ｒ_２、Ｒ_３、Ｒ_６、Ｒ_７、Ｒ_１０、Ｒ_１１、Ｒ_１４及びＲ_１５は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、さらに置換基を有していてもよい。
Ｚ_１、Ｚ_２、Ｚ_３、及びＺ_４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。但し、Ｚ_１、Ｚ_２、Ｚ_３、及びＺ_４のうち少なくとも１つは、イオン性親水性基を置換基として有する。
ｌ、ｍ、ｎ、ｐ、ｑ_１、ｑ_２、ｑ_３及びｑ_４は、それぞれ独立に、１又は２を表す。
Ｍ_１は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。）

（一般式（２）中、
Ｒ_１７及びＲ_１８はそれぞれ独立して水素原子、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ラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。
Ａは二価の連結基をそれぞれ表し、隣接するＲ_１７、Ｒ_１８、及びＡは互いに連結して環を形成しても良い。
Ｙ及びＺは、それぞれ独立してハロゲン原子、水酸基、スルホン酸基、カルボキシル基、アミノ基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のシクロアルキルオキシ基、置換若しくは無置換のアリロキシ基、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアラルキルオキシ基、置換若しくは無置換のアルケニルオキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のシクロアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテロ環アミノ基、置換若しくは無置換のアラルキルアミノ基、置換若しくは無置換のアルケニルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロ環チオ基、置換若しくは無置換のアラルキルチオ基、置換若しくは無置換のアルケニルチオ基を表す。但し、Ｙ、Ｚのうち少なくとも１つは、スルホン酸基、カルボキシル基、又はイオン性親水性基を置換基として有する基である。
ｍ、及びｎは１から３であり、且つｍとｎの和は２から４である。）
〔２〕
一般式（１）で表されるフタロシアニン染料におけるＲ_２、Ｒ_３、Ｒ_６、Ｒ_７、Ｒ_１０、Ｒ_１１、Ｒ_１４及びＲ_１５が、水素原子であることを特徴とする〔１〕に記載の着色組成物。
〔３〕
一般式（１）で表されるフタロシアニン染料におけるＺ_１、Ｚ_２、Ｚ_３、及びＺ_４が、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ことを特徴とする〔１〕又は〔２〕に記載の着色組成物。
〔４〕
一般式（１）で表されるフタロシアニン染料におけるｌ、ｍ、ｎ及びｐが１である〔１〕〜〔３〕のいずれか１項に記載の着色組成物。
〔５〕
一般式（１）で表されるフタロシアニン染料におけるｑ_１、ｑ_２、ｑ_３及びｑ_４が２である〔１〕〜〔４〕のいずれか１項に記載の着色組成物。
〔６〕
前記一般式（２）で表されるフタロシアニン染料が、一般式（２−１）で表されるフタロシアニン染料である〔１〕〜〔５〕のいずれか１項に記載の着色組成物。

（一般式（２−１）中、
Ｒ^２７及びＲ^２８はそれぞれ独立して水素原子、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ラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。
Ａは二価の連結基をそれぞれ表し、隣接するＲ^２７、Ｒ^２８、及びＡは互いに連結して環を形成しても良い。
Ｒ^２９、Ｒ^２１０、及びＲ^２１１はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、Ｒ^２１２は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。
ｍ、及びｎは１から３であり、且つｍとｎの和は２から４である。）
・ 〔７〕
一般式（１）で表されるフタロシアニン染料と、一般式（２）で表されるフタロシアニン染料との質量比が５０／５０〜１０／９０である〔１〕〜〔６〕のいずれか１項に記載の着色組成物。
〔８〕
一般式（１）で表されるフタロシアニン染料の含有量が１〜２０質量％である〔１〕〜〔７〕のいずれか１項に記載の着色組成物。
〔９〕
〔１〕〜〔８〕のいずれか１項に記載の着色組成物を含むインクジェット記録用インク。 [1]
A coloring composition comprising a phthalocyanine dye represented by the following general formula (1) and a phthalocyanine dye represented by the following general formula (2).

(In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group , Heterocyclic thio group, phosphoryl Group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ and Z ₄ 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. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2.
M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. )

(In general formula (2),
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 aralkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted Represents a heterocyclic group, a substituted or unsubstituted alkenyl group.
A represents a divalent linking group, and adjacent R ₁₇ , R ₁₈ , and A may be connected to each other to form a ring.
Y and Z are each independently a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted allyloxy group, Substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or unsubstituted Substituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkylthio group Substituted or unsubstituted arylthio Represents a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio group. However, at least one of Y and Z is a group having a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group as a substituent.
m and n are 1 to 3, and the sum of m and n is 2 to 4. )
[2]
In [1], R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ in the phthalocyanine dye represented by the general formula (1) are hydrogen atoms. The coloring composition as described.
[3]
Z ₁ , Z ₂ , Z ₃ and Z ₄ in the phthalocyanine dye represented by the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. The coloring composition according to [1] or [2], wherein the coloring composition represents a substituted heterocyclic group.
[4]
The coloring composition according to any one of [1] to [3], wherein l, m, n, and p in the phthalocyanine dye represented by the general formula (1) are 1.
[5]
The colored composition according to any one of [1] to [4], wherein q ₁ , q ₂ , q ₃ and q ₄ in the phthalocyanine dye represented by the general formula (1) are 2.
[6]
The coloring composition according to any one of [1] to [5], wherein the phthalocyanine dye represented by the general formula (2) is a phthalocyanine dye represented by the general formula (2-1).

(In general formula (2-1),
R ²⁷ and R ²⁸ are each independently 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 aryl group, substituted or unsubstituted Represents a heterocyclic group, a substituted or unsubstituted alkenyl group.
A represents a divalent linking group, and adjacent R ²⁷ , R ²⁸ , and A may be connected to each other to form a ring.
R ²⁹ , R ²¹⁰ , and R ²¹¹ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ²¹² represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group. Represents a cyclic group and has at least one ionic hydrophilic group as a substituent.
m and n are 1 to 3, and the sum of m and n is 2 to 4. )
・ [7]
Any one of [1] to [6], wherein the mass ratio of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is 50/50 to 10/90. The coloring composition as described in.
[8]
The coloring composition according to any one of [1] to [7], wherein the content of the phthalocyanine dye represented by the general formula (1) is 1 to 20% by mass.
[9]
Ink for inkjet recording containing the coloring composition of any one of [1]-[8].

  According to the present invention, there are provided a coloring composition and an ink jet recording ink that have good ozone fastness, high printing density, suppress bronze gloss, realize excellent hue, and have excellent storage stability over time. Provided.

  In the present invention, the substituent group A is defined as follows.

(Substituent group A)
Halogen atom (for example, chlorine atom, bromine atom); C1-C12 linear or branched alkyl group, C7-C18 aralkyl group, C2-C12 alkenyl group, C2-C2 12 linear or branched alkynyl groups, cycloalkyl groups having 3 to 12 carbon atoms which may have side chains, and cycloalkenyl groups having 3 to 12 carbon atoms which may have side chains ( Specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl): aryl group (for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl); heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyridyl) An alkyloxy group (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy); an aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3) -Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); acylamino groups (eg acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide); alkylamino groups (eg , Methylamino, butylamino, diethylamino, methylbutylamino); anilino group (eg, phenylamino, 2-chloroanilino; ureido group (eg, phenylureido, methylureido, N, N-dibutylureido)); Moylamino group (eg, N, N-dipropylsulfamoylamino); alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio); arylthio group (eg, phenylthio, 2-butoxy-5-t-octylphenylthio) , 2-carboxyphenylthio); alkyloxycarbonylamino group (for example, methoxycarbonylamino); sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane); carbamoyl group (for example, N -Ethylcarbamoyl, N, N-dibutylcarbamoyl); sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl groups (eg Tansulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl); heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy) An azo group (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); an acyloxy group (eg, acetoxy); a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino group (for example, phenoxycarbonyl) Amino); imide group (for example, N-succinimide, N-phthalimi); heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio) , 2-pyridylthio); sulfinyl group (eg, 3-phenoxypropylsulfinyl); phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); aryloxycarbonyl group (eg, phenoxycarbonyl); acyl group (For example, acetyl, 3-phenylpropanoyl, benzoyl); ionic hydrophilic group (for example, sulfo group, carboxyl group, thiocarboxyl group, sulfino group, phosphono group, dihydroxyphosphino group, quaternary ammonium group); other Cyano group, hydroxyl group, nitro group Amino group.

  The coloring composition of this invention contains the phthalocyanine dye represented by following General formula (1), and the phthalocyanine dye represented by General formula (2). The phthalocyanine dye represented by the general formula (1) is a dye that does not easily associate, whereas the phthalocyanine dye represented by the general formula (2) is a dye that easily associates. Although the mechanism is unclear, by using together with the phthalocyanine dye represented by the following general formula (1) and the phthalocyanine dye represented by the general formula (2), interaction occurs and association is appropriately controlled. Therefore, it is considered that the printing density and ozone resistance are excellent, and that the storage stability with time is excellent even in a high concentration aqueous solution.

[Phthalocyanine dye represented by formula (1)]
First, the phthalocyanine dye represented by the general formula (1) will be described in detail.

(In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group , Heterocyclic thio group, phosphoryl Group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ and Z ₄ 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. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2.
M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. )

In general formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an alkenyl. Group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group , Alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryl Oxycarbonylamino group, imide group, heterocycle It represents an OH group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent. Examples of the substituent include the substituents described in the above substituent group A.

Examples of the halogen atom represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ include a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

The aralkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group, and a 2-furyl group.

The alkylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As an alkoxy group when a substituent is removed, an alkoxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

The amide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an amide group having a substituent and an unsubstituted amide group. The amide group is preferably an amide group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.

The arylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

The sulfamoylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. A group is included. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include an N, N-dipropylsulfamoylamino group.

The alkylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. It is. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

The sulfamoyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

The alkoxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 includes} a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. It is. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The silyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a silyloxy group having a substituent and an unsubstituted silyloxy group. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.

The aryloxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. It is. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino A group is included. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimide group and an N-succinimide group.

The heterocyclic thio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 includes} a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. It is. The heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The phosphoryl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

The acyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The ionic hydrophilic groups represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ include sulfo group, carboxyl group, thiocarboxyl group, sulfino group, phosphono group, dihydroxy group A phosphino group, a quaternary ammonium group, and the like are included. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido, among others Group, sulfonamido group, carbamoyl group, sulfamoyl group and alkoxycarbonyl group are preferable, hydrogen atom, halogen atom and cyano group are particularly preferable, and hydrogen atom is most preferable.

In general formula (1), Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, It represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. Examples of the substituent include the substituents described in the above substituent group A.

The alkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms when a substituent is excluded. Examples of the substituent group, a hydroxyl group, an alkoxy group, a cyano group, an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), a sulfamoyl group _{(-SO 2 NHR, -SO 2 NRR} ') Sulfonylamino group (—NHSO ₂ R), —SONHR group, —SONRR ′ group, halogen atom and ionic hydrophilic group. (Note that R and R ′ represent an alkyl group and a phenyl group, and these may have a substituent. Examples of the substituent include an alkylamino group, a hydroxyl group, and an ionic hydrophilic group. R and R ′ may form a ring by a chemical bond.) Examples of the alkyl group include methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trimethyl. Fluoromethyl, 3-sulfopropyl and 4-sulfobutyl are included.

The cycloalkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

The aralkyl group represented by Z ₁ , Z ₂ , Z ₃ and Z ₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when a substituent is removed is preferable. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl. Examples of the substituent include an alkyl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), a sulfamoyl group (—SO ₂ NHR), A sulfonylamino group (—NHSO ₂ R), a halogen atom, and an ionic hydrophilic group are included (note that R and R ′ represent an alkyl group and a phenyl group, and these may also have an ionic hydrophilic group. Good).

The heterocyclic group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and may form a condensed ring with another ring. Good. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group may form a condensed ring with another ring. Examples of the heterocyclic group include, but are not limited to, the substitution position of the heterocyclic ring. Oxazole, benzoxazole, thiadiazole, oxadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzoisoxazole, thiophene, benzothiophene, furan, benzofuran, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine, Quinazoline, quinoxaline, triazine and the like are included. Examples of the substituent include an alkyl group (R-), an aryl group (R-), an alkoxy group (RO-), an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), and a sulfamoyl group. (—SO ₂ NHR), a sulfonylamino group (—NHSO ₂ R), a sulfonyl group (—SO ₂ R), an acylamino group (—NHCOR), a halogen atom, and an ionic hydrophilic group are included (note that R, R above) 'Represents an alkyl group or an aryl group, and these may have an ionic hydrophilic group or a substituent having an ionic hydrophilic group).

Z ₁ , Z ₂ , Z ₃ and Z ₄ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group. A substituted heterocyclic group is more preferred, and a substituted alkyl group is more preferred.

At least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

  In general formula (1), l, m, n and p each independently represent 1 or 2. That is, 4 ≦ l + m + n + p ≦ 8 is satisfied. Preferably, 4 ≦ l + m + n + p ≦ 6 is satisfied, and most preferably, each is 1 (1 = m = n = p = 1).

In general formula (1), q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2. In particular, q ₁ = q ₂ = q ₃ = q ₄ = 2 is preferable.

In General Formula (1), M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

What is preferable as M ₁ is a metal element other than a hydrogen atom, such as 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. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable. Preferred examples of the metal oxide include VO and GeO. Moreover, as a metal hydroxide, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc. are mentioned preferably. Further, as the metal _{halide, AlCl, SiCl 2, VCl,} VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.

[Synthesis of Phthalocyanine Dye Represented by General Formula (1)]
Examples of the phthalocyanine derivative represented by the general formula (1) include Japanese Patent Application Laid-Open No. 2002-249677 and Shirai-Kobayashi, published by IPC Co., Ltd. “Phthalocyanine—Chemistry and Function” (P. 1-62), C. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (P. 1-54), etc., can be synthesized by combining quoted or similar methods.

The compounds represented by the general formulas (a) -1 to (a) -4 are α-substituted (when R _{1 to} R ₁₆ in the following general formula (IV) are respectively in the 1st to 16th positions, Phthalocyanine compounds having specific substituents at the 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position).

The phthalocyanine dye represented by the general formula (1) of the present invention has a α-position substitution type (1 and / or 4 position, 5 and / or 8 position, 9 and or 12 position, 13 and or 16 position specific substituent Phthalocyanine compound).
It is important for good fastness that the phthalocyanine dye represented by the general formula (1) has a specific substituent represented by —SO—Z and / or SO ₂ —Z.

  Specific examples of the phthalocyanine dye represented by the general formula (1) are shown below using the following general formula (IV), but the phthalocyanine dye used in the present invention is not limited to the following examples.

[Azaphthalocyanine dye represented by formula (2)]

(In general formula (2),
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 aralkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted Represents a heterocyclic group, a substituted or unsubstituted alkenyl group.
A represents a divalent linking group, and adjacent R ¹⁷ , R ¹⁸ , and A may be connected to each other to form a ring.
Y and Z are each independently a halogen atom, hydroxyl group, sulfonic acid group, carboxyl group, amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyloxy group, substituted or unsubstituted aryloxy group Substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or Unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkylthio Group, substituted or unsubstituted aryl O represents group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio group. However, at least one of Y and Z is a group having a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group as a substituent.
m and n are 1 to 3, and the sum of m and n is 2 to 4. )

The substituted or unsubstituted alkyl group represented by R ¹⁷ and R ¹⁸ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. More preferred is an alkyl group of 4. Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable. As an alkyl group, methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl is preferable, methyl or n-propyl is more preferable, and n-propyl is still more preferable.
R ²⁷ and R ²⁸ preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.

The cycloalkyl group represented by R ¹⁷ and R ¹⁸ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. A cyclohexyl group is preferred as an example of a cycloalkyl group.
Examples of the aralkyl group represented by R ¹⁷ and R ¹⁸ include a substituted aralkyl group and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group are preferably a benzyl group and a 2-phenethyl group.

The substituted or unsubstituted aryl group represented by R ¹⁷ and R ¹⁸ is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include substituent group A, and an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group are preferable. As the aryl group, phenyl or naphthyl is preferable.

The substituted or unsubstituted heterocyclic group represented by R ¹⁷ and R ¹⁸ is preferably a 5-membered or 6-membered heterocyclic group. Substituent group A is mentioned as a substituent, and an ionic hydrophilic group is contained. As the heterocyclic group, a 2-pyridyl group, a 2-thienyl group and a 2-furyl group are preferable.

The alkenyl group represented by R ¹⁷ and R ¹⁸ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Preferred examples of the alkenyl group include a vinyl group and an allyl group.

The aryloxy group represented by R ¹⁷ and R ¹⁸ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Preferable examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  A halogen atom represented by Y and Z, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted Aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group Substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted hetero Ring thio group, substituted or unsubstituted Aralkylthio groups, the substituted or unsubstituted alkenylthio group, can be exemplified those mentioned substituent group A.

  The divalent linking group represented by A is an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SOn- (n is 0, 1, 2), -NR- (R is a hydrogen atom, an alkyl group, Represents an aryl group), -O-, and a divalent group obtained by combining these linking groups, and further include an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, a halogen atom, You may have substituents, such as a hydroxyl group, a carboxyl group, a sulfamoyl group, a carbamoyl group, and a sulfonamide group. An alkylene group is preferable, and an ethylene group and an n-propylene group are preferable.

  The phthalocyanine dye represented by the general formula (2) is preferably a phthalocyanine dye represented by the following general formula (2-1).

(In general formula (2-1),
R ²⁷ and R ²⁸ are each independently 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 aryl group, substituted or unsubstituted Represents a heterocyclic group, a substituted or unsubstituted alkenyl group.
A represents a divalent linking group, and adjacent R ²⁷ , R ²⁸ , and A may be connected to each other to form a ring.
R ²⁹ , R ²¹⁰ , and R ²¹¹ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ²¹² represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group. Represents a cyclic group and has at least one ionic hydrophilic group as a substituent. It is a group having a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group as a substituent.
m and n are 1 to 3, and the sum of m and n is 2 to 4. )

A, R ²⁷ and R ²⁸ have the same meanings as A, R ¹⁷ and R ¹⁸ in formula (1), and preferred ones are also the same.
The substituted or unsubstituted alkyl group represented by R ²⁹ , R ²¹⁰ and R ²¹¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, More preferred are alkyl groups having 1 to 4 numbers. Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable. As an alkyl group, methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl is preferable, methyl or n-propyl is more preferable, and n-propyl is still more preferable.
R ²⁷ and R ²⁸ preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.

R ²¹² preferably represents a substituted aryl group, and examples of the substituent include Substituent Group A, which has at least one ionic hydrophilic group as a substituent. The substituent is preferably an ionic hydrophilic group, preferably a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group, more preferably a carboxyl group and a sulfo group. A sulfo group is more preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

R ²¹² represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and more preferably a substituted alkyl group or a substituted aryl group.
R ²¹² is preferably an aryl group substituted with 1 to 3 ionic hydrophilic groups, preferably an aryl group substituted with 2 ionic hydrophilic groups (preferably a carboxyl group or a sulfo group). It is more preferable.

  Specific examples of the substituent containing the linking group A in the general formula (2) are given below, but the present invention is not limited to these specific examples.

  Specific examples of the phthalocyanine dye represented by the general formula (2) are shown below, but the phthalocyanine dye used in the present invention is not limited to the following examples.

[Synthesis of Phthalocyanine Dye Represented by General Formula (2)]
The phthalocyanine derivative represented by the general formula (2) can be synthesized, for example, by the method described in JP-A No. 2004-329677.

(Coloring composition)
The coloring composition of this invention contains the phthalocyanine dye represented by the said General formula (1), and the phthalocyanine dye represented by the said General formula (2). By using the α-position-substituted dye of the general formula (1) and the phthalocyanine dye of the general formula (2) having a specific substituent, the ratio between the α-position and the β-position is adjusted not between the molecules but between the molecules. As a result, it is possible to achieve both good fastness and high print density.
The colored composition of the present invention can be preferably used as a colored composition for image formation. Applications of the colored composition of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal transfer type images including ink jet recording materials described in detail below. Recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, thermal transfer type image recording materials, electrophotographic methods In particular, an ink jet recording material is preferable. Further, it can also be applied to dyeing solutions for dyeing various fibers of color filters used in solid-state imaging devices such as LCDs and CCDs described in US Pat. No. 4,808,501 and JP-A-6-35182. .
The phthalocyanine dye used in the present invention is used by adjusting physical properties such as solubility and heat transfer properties suitable for the intended use with a substituent. The phthalocyanine dye used in the present invention can be used in a uniform dissolved state or a dispersed dissolved state such as an emulsified dispersion depending on the system used.

  In the coloring composition, the mass ratio of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is preferably 50/50 to 10/90. By making the mass ratio of the dye within the above range, the colored composition is excellent in stability over time (viscosity change, precipitation, etc.) at a high concentration, and is excellent in ozone fastness of a print sample using the colored composition. Further, it is possible to obtain a feature that the print density is excellent.

  Moreover, it is preferable that content of the phthalocyanine dye represented by General formula (1) in a coloring composition is 0.1-20 mass%, It is more preferable that it is 1-20 mass%, 1-10 More preferably, it is mass%. When the content is 0.1% by mass or more, the color composition has excellent stability over time and the printing density, and when the content is 20% by mass or less, the ozone fastness of the printing sample is excellent.

  Moreover, it is preferable that content of the phthalocyanine dye represented by General formula (2) in a coloring composition is 0.1-20 mass%, It is more preferable that it is 1-20 mass%, 1-10 More preferably, it is mass%. When the content is 0.1% by mass or more, the ozone fastness of the print sample is excellent, and further, the print density is excellent. Moreover, if it is 20 mass% or less, the temporal stability in the high density | concentration of a coloring composition will be excellent.

  In the present invention, the dye content in the coloring composition (that is, the total amount of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2)) is 15 to 20% by mass. It was found that even when a concentrated dye solution was used, precipitation of the dye over time could be suppressed. For this reason, the colored composition of the present invention is also useful as a dense inkjet ink.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described. The ink for inkjet recording of the present invention contains the above colored composition. The ink for inkjet recording can be produced by dissolving and / or dispersing the phthalocyanine compound 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 penetration enhancers, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants, etc. 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, Nos. VII to I, J; 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-59-157636, 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 compound and the phthalocyanine compound according to the present invention are dispersed in an aqueous medium, they are described in JP-A Nos. 11-286637, 2000-78491, 2000-80259, 2000-62370, etc. As described above, colored fine particles containing a pigment and an oil-soluble polymer can be dispersed in an aqueous medium, or Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 2000-203857 can be used. It is preferable to disperse the compound of the present invention dissolved in a high boiling point organic solvent in an aqueous medium as described in each specification. The specific method for dispersing the compound 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. be able to. Alternatively, the phthalocyanine compound 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 compound is preferably contained in an amount of 0.2 parts by mass or more and 20 parts by mass or less. In addition, in the inkjet ink of the present invention, other pigments may be used in combination with the phthalocyanine compound. 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 40 cp or less. The surface tension is preferably 20 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 type 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 and 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 heteryl 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, Polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo and 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 co-paper, fabric, 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 .mu.m 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 polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. 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 resistance 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, 62-1316648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

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

  The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

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 NaOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 μm to prepare an ink solution for cyan.

1.5 g of phthalocyanine dye (Compound 1A)
Phthalocyanine dye (compound 4A) 3.5 g
Diethylene glycol 2g
Glycerin 12g
Diethylene glycol monobutyl ether 23g
2-pyrrolidone 8g
1.79 g of triethanolamine
Benzotriazole 0.006g
Surfynol 465 (trade name, manufactured by Air Products) 0.85 g
PROXEL XL2 (manufactured by FUJIFILM Imaging Colorant) 0.18g

(Examples 2-6, Comparative Examples 1-5)
Ink liquids of Examples 2 to 6 and Comparative Examples 1 to 5 were prepared in the same manner as the ink liquids of Example 1 except that the phthalocyanine dye and the dye addition amount were changed as shown in Table 9 below. .

<Image recording and evaluation>
The following evaluation was performed about the ink for inkjets of each of the above Examples (Examples 1 to 6) and Comparative Examples (Comparative Examples 1 to 5). The results are shown in Table 9. For image recording, each ink-jet ink is recorded on photo glossy paper (PT-101, Canon) and plain paper (GF500, Canon) with an inkjet printer (manufactured by EPSON Corporation; PM-700C). did.

(Ozone resistance)
The photo-glossy paper on which the image has been formed is left in a box set at an ozone gas concentration of 5 ± 0.1 ppm, room temperature, in a dark place for one day, and the image density before and after being left under ozone gas is measured by 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)
When the reflection density of plain paper at 100% printing density is measured using a reflection densitometer (X-Rite 310TR), the printing density is 1.10 or more when A is 1.05 or more and less than 1.10. Was evaluated in three stages, with B being less than 1.05 and C being less than 1.05.

(Bronze gloss)
The highest density part of the printed sample is visually observed under a white fluorescent lamp. A case where no bronze-like luster is observed is B, a case where it is slightly observed is B, and a case where it is clearly observed is shown in three stages. evaluated.

(Hue)
The printed sample was visually observed and evaluated in three stages: A for pure cyan, B for cyan close to reddish blue, and C for clear blue.

(Example 101)
Deionized water was added to the following components to make 33.3 g, and the mixture was stirred for 1 hour while heating at 50 ° C. Thereafter, the pH was adjusted to 9 with NaOH 10 mol / L to prepare a concentrated aqueous solution.

1.5 g of phthalocyanine dye (Compound 1A)
Phthalocyanine dye (compound 4A) 3.5 g
Diethylene glycol 2g
Glycerin 12g
Diethylene glycol monobutyl ether 23g
2-pyrrolidone 8g
1.79 g of triethanolamine
Benzotriazole 0.006g
Surfynol 465 (trade name, manufactured by Air Products) 0.85 g
PROXEL XL2 (manufactured by FUJIFILM Imaging Colorant) 0.18g

(Examples 102 to 106, Comparative Examples 101 to 105)
Ink liquids of Examples 102 to 106 and Comparative Examples 101 to 105 were prepared in the same manner as in the preparation of the concentrated aqueous solution of Example 101, except that the phthalocyanine dye and the dye addition amount were changed as shown in Table 10 below. .

(Storage stability over time)
Concentrated aqueous solutions of the above Examples (Examples 101 to 106) and Comparative Examples (Comparative Examples 101 to 105) are stored in a sealed and stationary state for 2 weeks at room temperature and kept in a dissolved state visually. A and B in which precipitation or separation of the dye occurred were evaluated.

  The ink for inkjet recording of the present invention was found to exhibit a high print density, suppress bronze gloss, and achieve an excellent hue while maintaining equivalent ozone resistance as compared with the comparative ink. . Moreover, it turned out that it is excellent also in storage stability with time.

  The structures of the compounds used in the examples are shown below.

Claims (5)

A coloring composition comprising a phthalocyanine dye represented by the following general formula (1) and a phthalocyanine dye represented by the following general formula (2).

(In general formula (1),
_{R 2, R 3, R 6} , R 7, R 10, R 11, R 14 and _{R 15} represents a hydrogen atom.
Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent a substituted or unsubstituted alkyl group . However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has a sulfo group as a substituent.
l, m, n, and p represent ₁ ; q ₁ , q ₂ , q _3, and q ₄ represent 2 ;
M ₁ represents Cu . )

(In general formula (2),
R ₁₇ and _{R 18} represents a water MotoHara child.
A is to each table an alkylene group.
Y and Z represent each independently an amino group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group. However, at least one of Y and Z is a group having a sulfo group as a substituent. m and n are 1 to 3, and the sum of m and n is 2 to 4. ) The coloring composition according to claim 1 , wherein the phthalocyanine dye represented by the general formula (2) is a phthalocyanine dye represented by the general formula (2-1).

(In general formula (2-1),
R ²⁷ and ^{R 28} represents a hydrogen atom.
A is to each table an alkylene group.
R ²⁹ , R ²¹⁰ , and R ²¹¹ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ²¹² represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group. Represents a cyclic group and has at least one sulfo group as a substituent.
m and n are 1 to 3, and the sum of m and n is 2 to 4. ) The coloring composition according to claim 1 or 2 , wherein a mass ratio of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is 50/50 to 10/90. Content of the phthalocyanine dye represented by General formula (1) is 1-20 mass%, The coloring composition of any one of Claims 1-3 . An ink for inkjet recording comprising the colored composition according to any one of claims 1 to 4 .