JP2003012952A - Production method for phthalocyanine colorant, phthalocyanine colorant, colored composition, ink, ink for ink jet recording, ink set for ink jet recording, ink jet recording method, and container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for a novel phthalocyanine colorant excellent in solubility; a phthalocyanine colorant; a colored composition containing the colorant; and an ink, an ink for ink jet recording, an ink set for ink jet recording, an ink jet recording method, and a container exhibiting a high recording stability even under various environmental conditions. SOLUTION: In the production method, a phthalocyanine colorant is produced by reacting at least two compounds selected from among phthalonitriles different in soluble groups or in their precursors and phthalic acid derivatives different in soluble groups or in their precursors with a metal derivative. In addition, there are provided a phthalocyanine colorant produced by the method; a colored composition containing the colorant; and an ink, an ink for ink jet recording, an ink set for ink jet recording, an ink jet recording method, and a container containing the colored composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phthalocyanine dye having improved solubility and excellent fastness, a method for producing the same, and a coloring composition containing the phthalocyanine dye,
The present invention relates to an ink containing the coloring composition, an inkjet recording ink, an inkjet recording ink set, an inkjet recording method, and a container.

[0002]

2. Description of the Related Art In recent years, as an image recording material, a material for forming a color image has been mainly used, and specifically, an ink jet recording material, a heat transfer recording material, and an electrophotographic recording material. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc. are widely used. Further, a color filter is used for recording and reproducing a color image in an image pickup device such as a CCD in a photographing device and in an LCD or a PDP in a display. These color image recording materials and color filters use dyes (dyes and pigments) of three primary colors of so-called additive color mixture method and subtractive color mixture method in order to reproduce or record a full color image, but a preferable color reproduction range. It is the actual situation that there are few dyes that have absorption characteristics capable of achieving the above and can withstand various use conditions and environmental conditions, and that have good solubility, and improvement is strongly desired.

The ink jet recording method is rapidly spreading and further developing because of low material cost, high speed recording, low noise during recording, and easy color recording. is there. Ink jet recording methods include a continuous method for continuously ejecting droplets and an on-demand method for ejecting droplets according to an image information signal. There are a method of ejecting liquid, a method of generating bubbles in the ink by heat to eject a droplet, a method of using ultrasonic waves, or a method of sucking and ejecting a droplet by electrostatic force. Further, as the ink for inkjet recording,
Water-based ink, oil-based ink, or solid (melting type) ink is used.

The dye used in such ink jet recording ink has good solubility or dispersibility in a solvent and high density recording is possible.
Good hue, active gas in light, heat and environment (N
Ox, ozone, and other oxidizing gases such as SOx), robustness against water and chemicals, good fixability to the image receiving material, and less bleeding,
It is required that the ink be excellent in storability, have no toxicity, have high purity, and be inexpensively available. However, it is extremely difficult to search for a dye that meets these requirements at a high level.
In particular, it has a good cyan hue and is robust to light, humidity, and heat, and when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles, It is strongly desired to be robust against oxidizing gases such as ozone.

Examples of cyan dye skeletons used in such ink jet recording inks include phthalocyanine-based, anthraquinone-based and triphenylmethane-based dyes, and the phthalocyanine-based dyes are typical.

The most widely reported and utilized representative phthalocyanine dyes include phthalocyanine derivatives classified by the following. Direct Blue 86 or Direct B
copper phthalocyanine dyes such as lue 87 {eg,
_{Cu-Pc- (SO 3 Na)} m: a mixture of m = 1~4} Direct Blue 199, and JP 62-
190273, JP 63-28690, JP 6
3-306075, JP-A-63-306076, JP-A-2-131983, JP-A-3-122171,
Phthalocyanine dyes described in JP-A-3-200883, JP-A-7-138511 and the like (for example, Cu
_{-Pc- (SO 3 Na) m (} SO 2 NH 2) n: m + n = 1
A mixture of ~ 4}

Japanese Patent Laid-Open Nos. 63-210175 and 6
3-37176, JP-A-63-304071, JP-A-5-171085 and the like, WO 00/081
Phthalocyanine dyes described in No. 02 and the like {for example, Cu-
_{Pc- (CO 2 H) m (} CONR 1 R 2) n: m + n = 0~
Number of 4} JP-A-59-30874, JP-A-1-126381
JP-A-1-190770 and JP-A-6-16982.
Japanese Patent Application Laid-Open No. 7-82499, Japanese Patent Application Laid-Open No. 8-34942.
No. 8-60053 and No. 8-113745.
JP-A-8-310116 and JP-A-10-1400.
63, JP-A-10-298463, and JP-A-11-2.
No. 9729, JP-A No. 11-320921 and the like,
EP173476A2, EP468649A1, E
P559309A2, EP596383A1, DE
3411476, US 6086955, WO 99
/ 13009 Patent, phthalocyanine dyes described in GB2341868A No., etc. _{{e.g., Cu-Pc- (SO 3 H} ) m
(SO ₂ NR ₁ R ₂ ) _n : m + n = 0 to 4 and m ≠
0}

Japanese Unexamined Patent Publication Nos. 60-208365 and 6
1-2772, JP-A-6-57653, and JP-A-8-
60052, JP-A-8-295819, JP-A-10
-130517, Japanese Patent Laid-Open No. 11-72614, Japanese Patent Publication No. 11-515047, Japanese Patent Publication No. 11-515048, etc., EP196901A2, WO95 / 292.
08, WO98 / 49239, WO98 / 4924
0, WO99 / 50363, WO99 / 67334
Phthalocyanine dyes described in, for example, No.
_{- (SO 3 H) l (} SO 2 NH 2) m (SO 2 NR 1 R 2) n:
1 + m + n = 0 to 4}} JP-A-59-22967, JP-A-61-18557
6, JP-A-1-95093, and JP-A-3-19578.
No. 3, etc., EP 649881 A1, WO 00
/ 08101 Patent, phthalocyanine dyes {e.g. described in such Patent WO00 / 08103, Cu-Pc- ( SO 2 NR 1
R ₂ ) _n : n = 1 to 5}

Direc which is currently widely used
t Blue 87 or Direct Blue 19
The phthalocyanine dyes typified by No. 9 and described in the above publications are characterized in that they are superior in light resistance to magenta and yellow, but they are liable to cause problems due to the solubility of dyes. In many cases, defects cause manufacturing troubles, and insoluble matter precipitates during product storage and use, causing problems. Particularly, in the above-mentioned ink jet recording, there is a problem that the deposition of dye causes clogging of the print head and ejection failure, resulting in remarkable deterioration of the printed image.

Further, it is a serious problem that an oxidizing gas such as ozone, which has been often taken up as an environmental problem these days, easily causes fading, resulting in a large decrease in print density.

At present, the field of use of ink jet recording is rapidly expanding, and when it is used more widely in general households, SOHO, business fields, etc., it is exposed to various use conditions and use environments. In many cases, troubles due to poor solubility of dyes may occur, or fading of printed images may become a problem due to exposure to light or active gas in the environment. Therefore, a dye and an ink composition having a particularly good hue, excellent light fastness and fastness to active gases in the environment (SOx in addition to oxidizing gases such as NOx and ozone) and having high solubility are obtained. Increasingly desired.

However, it is extremely difficult to search for a phthalocyanine dye and a cyan ink containing the same which satisfy these requirements at a high level.

So far, phthalocyanine dyes having ozone gas resistance have been disclosed in JP-A-3-103484,
JP-A-4-39365, JP-A-2000-300309
Although each of the publications such as No. has been disclosed, it is the current situation that none of them achieves both hue and light and oxidizing gas fastness at the same time. In particular, there have been no reports on the properties of dyes that serve as guidelines for ozone gas resistance.

Further, in general, phthalocyanine dyes (compounds) are represented by WO 00/17275 and WO 00/0810.
3, No. 00/08101, No. 98/41853, and Japanese Patent Laid-Open No. 10-36471.
When an unsubstituted phthalocyanine compound is sulfonated and used as a water-soluble dye, it is used as it is as an alkali metal salt of the sulfonated compound, for example, a sodium salt, and when it is derived into an oil-soluble dye, it is sulfonated after sulfonation. It is possible to use the one synthesized through the cationization and amidation reaction. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonates is also difficult to control. Therefore, when the sulfo group is introduced under such reaction conditions, the position and the number of the sulfo group introduced into the product cannot be specified, and a mixture having different numbers of substituents and different substitution positions is always provided. Then, a component having a low solubility, for example, a component having only one or two sulfonated phthalocyanine nuclei, is mixed in the mixture, and the oil-soluble dye is used even when used as a water-soluble dye. Even when it is induced to, the solubility tends to be insufficient, and improvement of the solubility is desired.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and achieve the following objects. That is, the first object of the present invention is to have excellent absorption properties in color reproducibility as a pigment of the three primary colors, and to have sufficient fastness to light, heat, humidity and active gas in the environment, It is to provide a method for producing a novel phthalocyanine dye having excellent solubility, a phthalocyanine dye obtained by the production method, and a coloring composition using the phthalocyanine dye. A second object of the present invention is to include the coloring composition, which is excellent in ink storage stability and clogging recovery, has a good hue, and further has an active gas in light and environment,
In particular, an ink, an inkjet recording ink, which is capable of forming an image having high robustness against ozone gas and has high recording stability even when used under various environmental conditions, and an inkjet including the inkjet recording ink A recording ink set, an inkjet recording method using the inkjet recording ink, and a container for containing the inkjet recording ink.

[0016]

Means for Solving the Problems The present inventors have studied in detail a phthalocyanine dye derivative having good hue and solubility and high light fastness and gas fastness (particularly ozone gas). The inventors have found that a phthalocyanine dye having a specific structure synthesized by a specific synthesis method, which has not been known so far, can solve the above-mentioned problems, and completed the present invention. That is, the present invention is

<1> At least two kinds selected from a phthalonitrile having a different soluble group or a precursor thereof and a phthalic acid derivative having a different soluble group or a precursor thereof,
A method for producing a phthalocyanine dye, which comprises producing a phthalocyanine dye obtained by reacting with a metal derivative.

<2> The phthalocyanine dye has a phthalocyanine skeleton having four benzene rings, and the four benzene rings have Hammett's substituent constant σ.
at least one different soluble group having a p-value of 0.4 or more is present <1
The method for producing the phthalocyanine dye according to the item>.

<3> A phthalocyanine dye obtained by the method for producing a phthalocyanine dye according to <1> or <2>. <4> A coloring composition comprising the phthalocyanine dye according to <3>.

<5> An ink containing the coloring composition according to <4>. <6> An ink for inkjet recording containing the coloring composition according to <4>.

<7> An ink jet recording ink set comprising two or more ink jet recording inks having different dye concentrations, wherein the ink jet recording ink is the ink jet ink according to <6>. And an ink set for inkjet recording.

<8> Ink jet recording, characterized in that energy is applied to the ink for ink jet recording according to <6> to eject liquid droplets of the ink onto an image receiving material to record an image on the surface of the image receiving material. Is the way. <9> A container containing the inkjet recording ink according to <6>.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Method for Producing Phthalocyanine Dye, Phthalocyanine Dye] The method for producing a phthalocyanine dye of the present invention comprises a phthalonitrile (o-
Phthalonitrile) and a phthalic acid derivative having a soluble group or a precursor thereof introduced thereinto (hereinafter, the phthalonitrile and the phthalic acid derivative are referred to as “phthalic acid derivative”) and a metal derivative are reacted to produce a phthalocyanine dye. Is the way. In this production method, a soluble group or a precursor thereof is introduced into a phthalic acid derivative which is a raw material in advance, so that, for example, in the structure of the obtained phthalocyanine dye,
It is possible to introduce a soluble group or its precursor without omission into one benzene ring, or to introduce a desired number of soluble groups in a desired number. Furthermore, as will be described later, the oxidation potential can be adjusted to be high (noble) by introducing an electron-withdrawing soluble group. Therefore, a phthalocyanine dye having excellent absorption properties with excellent color reproducibility as a three-primary-color dye, and having sufficient fastness to active gas in light, heat, humidity, and environment, and having excellent solubility is obtained. It can be manufactured.

Furthermore, in the method for producing a phthalocyanine dye of the present invention, the soluble group or its precursor is different.
It is characterized by using at least two kinds of phthalic acid derivatives. This results in a mixture of phthalocyanine dyes having different types of soluble groups and different bonding positions, having a distribution determined by the charging ratio of the phthalic acid derivative used, and thus the solubility is further improved. Therefore, the present invention also provides a method for improving the solubility of phthalocyanine dyes. As a result, the ink jet recording ink using the phthalocyanine dye of the present invention has improved storage stability and clogging recovery.

In the method for producing a phthalocyanine dye according to the present invention, preferably, as a phthalic acid derivative as a raw material, a phthalonitrile compound (the following compound A), a diiminoisoindoline compound (the following compound B), a phthalic acid compound is used. A compound and its salt (compound C below) and a phthalic anhydride compound (compound D below) can be used.

A phthalocyanine dye can be synthesized by reacting at least two kinds of phthalic acid derivatives having different soluble groups or precursors thereof with a metal derivative represented by the following general formula (I) as a metal derivative. Further, when X ′ in the compounds A to D as the phthalic acid derivative as a raw material is a precursor of a soluble group, the phthalocyanine dye of the present invention is synthesized by converting the phthalocyanine ring into a soluble group after forming. be able to.

[0027]

[Chemical 1]

General formula (I): M- (Z) d

In the above compounds A to D, X'represents a soluble group or a precursor thereof. In the general formula (I), M represents a hydrogen atom, a metal atom, or an oxide, hydroxide or halide thereof. Z represents a monovalent or divalent ligand such as a halogen atom, an acetate anion, acetylacetonate, or oxygen. d represents an integer of 1 to 4.

A phthalic acid derivative as a raw material (compounds A to
D) will be described. The soluble group is a substituent that imparts solubility to the phthalocyanine dye. When a solubilizing group imparts water solubility to a phthalocyanine dye, it represents a hydrophilic group. On the other hand, when the oil solubility is imparted to the phthalocyanine dye by the soluble group, it represents a hydrophobic group. The phthalocyanine dye of the present invention may be water-soluble or oil-soluble.

Examples of the hydrophilic group include an ionic hydrophilic group or a substituent having an ionic hydrophilic group substituted. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group. Of these, a sulfo group and a carboxyl group are preferable. The sulfo group and the carboxyl group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, sodium ion, potassium ion) and organic cation (eg, triethylammonium). Ion, tetramethylguanidinium ion).

As the hydrophobic group, an aliphatic group having 8 to 20 carbon atoms, an aromatic group having 8 to 20 carbon atoms, and a sulfamoyl group having a partial structure thereof, a sulfonyl group,
It represents a sulfinyl group, a sulfenyl group, a carbamoyl group, an acyl group, an ester group, an alkoxy group, an aryloxy group, an acylamino group, and an amino group. The aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The aromatic group means an aryl group and a substituted aryl group.
The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

The precursor of the soluble group represents a substituent which can be converted into a soluble group by a reaction after forming a phthalocyanine ring. As such a substituent, a hydroxyl group, a halogen atom, a mercapto group, an amino group, an acylamino group,
Examples thereof include reactive substituents such as an alkoxycarbonyl group, an alkenyl group and an imide group, or a substituent having them as a substituent.

In compounds A to D, X ′ is preferably a hydrophilic group, and —SO ₂ —R ₁ or —SO ₂ NR ₂ R
₃ is particularly preferred. R ₁ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are most preferable.
R ₂ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, a substituted heterocycle Most preferred are groups. R ₃ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are most preferable.

In compounds A to D, a represents the number of substituents of X'and is an integer of 1 to 4. b represents the number of substituents of Y, and represents an integer satisfying the relationship of a + b = 4. Preferably, a is 1 or 2, and more preferably 1. When a is 1 or 2, the position to be substituted by X ′ is the 4,5-position in the compounds A and C and the 5- and 6-positions in the compounds B and D (that is, the position marked with *, hereinafter referred to as the β position). Preferably there is.

In compounds A to D, Y represents a monovalent substituent. Examples of the monovalent substituent include a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group and an alkoxy group. Group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo Group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a phosphoryl group, and an acyl group, each of which further has a substituent. May be. Of these, particularly preferred are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group and an alkoxycarbonyl group, and particularly a hydrogen atom. , A halogen atom and a cyano group are preferable, and a hydrogen atom is most preferable. Further, the number of carbon atoms contained in this monovalent substituent is preferably less than 8.

When each of the above substituents further has a substituent, the substituent is preferably a halogen atom, a heterocyclic group, a cyano group, a hydroxyl group,
Nitro group, carboxyl group, acylamino group, ureido group, sulfamoylamino group, alkyloxycarbonyl group, alkyloxycarbonylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, sulfonyl group, acyloxy group, carbamoyloxy group, imide Group, heterocyclic thio group, and acyl group.

Specific examples of the phthalonitrile compound (Compound A) include 4-sulfophthalonitrile and 4- (3-
Sulfopropylsulfonyl) phthalonitrile, 4,5-
Bis (3-sulfopropylsulfonyl) phthalonitrile may be mentioned.

Specific examples of the diiminoisoindoline compound (compound B) include 3-amino-1-imino-1H.
-Isoindole-5-sulphonic acid.

Specific examples of the phthalic acid compounds and salts thereof (compound C below) include trimellitic acid, 4-sulfophthalic acid and 4- (3-sulfopropylsulfonyl) phthalic acid.

Specific examples of the phthalic anhydride compound (compound D) include trimellitic anhydride and 4-sulfophthalic anhydride.

The metal derivative (metal derivative represented by the general formula (I)) will be described. In the general formula (I), M represents a hydrogen atom, a metal atom, or an oxide, hydroxide or halide thereof. As the metal atom, Li, Na,
K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo,
W, Mn, Fe, Co, Ni, Ru, Rh, Pd, O
s, Ir, Pt, Cu, Ag, Au, Zn, Cd, H
g, Al, Ga, In, Si, Ge, Sn, Pb, S
b, Bi and the like.

Examples of the oxide include VO and GeO. As the hydroxide, Si (OH) ₂ , Cr (O
H) ₂ , Sn (OH) _{2 and the} like. As the halide, AlCl, SiCl ₂ , VCl, VCl ₂ , VO
Cl, FeCl, GaCl, ZrCl, etc. may be mentioned.
Among them, M is preferably Cu, Ni, Zn, Al or the like, and most preferably Cu. Z is a monovalent or divalent halogen atom, acetate anion, acetylacetonate, oxygen, etc.
A valent ligand is shown, and d is an integer of 1 to 4.

In the general formula (I), Z represents a monovalent or divalent ligand such as a halogen atom, an acetate anion, acetylacetonate or oxygen, and d represents an integer of 1 to 4.

Specific examples of the metal derivative (metal derivative represented by the general formula (I)) include Al, Si, Ti, V and M.
n, Fe, Co, Ni, Cu, Zn, Ge, Ru, R
halides such as h, Pd, In, Sn, Pt, and Pb,
Examples thereof include carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides and complexes. More specifically,
Copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride , Vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, manganese acetylacetone, manganese chloride, lead chloride, lead acetate, indium chloride,
Examples thereof include titanium chloride and tin chloride.

With respect to the preferable combination of substituents of the phthalocyanine dye of the present invention, a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and a compound in which more various substituents are the above-mentioned preferable group is preferable. Compounds in which all the substituents are the above-mentioned preferable groups are more preferable, and most preferable. The most preferred phthalic acid derivative of the present invention, that is, when a = 1, a soluble group is substituted at the β-position (4,5-positions in the compounds A and C, 5 and 6-positions in B and D)
A phthalocyanine dye prepared from Y being a hydrogen atom and M being Cu is represented by the following general formula (II) when synthesized using, for example, four different phthalic acid derivatives. It General formula (II): Cu-Pc- (X1) k (X2) l
(X3) m (X4) n

In the general formula (II), Cu-Pc represents copper phthalocyanine, and k, l, m, and n are numbers of 0 or more that give a total sum of 4, and X1, X2, X.
3, X4 represent mutually different soluble groups substituted at the β-position.

Although the cause is not clear in detail, the dye having the soluble group introduced only at the β-position tends to be superior in hue, light fastness, ozone gas resistance and the like as compared with other dyes. . In this case, as the soluble group X and the substituent Y, it is preferable from the viewpoint of synthesis to select a substituent having a large electron withdrawing property as the soluble group X.

The phthalocyanine dye (general formula (I) obtained by the method for producing a phthalocyanine dye of the present invention is described below.
Specific examples (exemplified compounds 1 to 59) of the phthalocyanine dye represented by are shown below, but the present invention is not limited to these specific examples. In addition, the numerical values in parentheses in the columns of R ¹ and R ² in Tables 1 to 6 and the lower part of the chemical formulas of Chemical formulas 2 and 3 represent Hammett's substituent constant σp values described later. Further, the underlined numerical values in the lower right part of the chemical formulas of Chemical formulas 2 and 3 indicate the oxidation potential described later.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Chemical 2]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Chemical 3]

According to the synthetic method of the present invention, a desired number of combinations of soluble groups can be introduced. In the method for producing a phthalocyanine dye of the present invention, the above,
By selecting a substituent having a large electron-withdrawing property as the soluble group X or the substituent Y, the oxidation potential of the obtained phthalocyanine dye can be adjusted to be high (noble), and an active gas such as ozone or singlet oxygen (for example, oxidation) can be adjusted. It is possible to further suppress the reactivity to (active gas) and to obtain a dye having resistance to active gas.

As a scale showing such electron-withdrawing property,
The Hammett's substituent constant σp value (hereinafter simply referred to as “σp value”) can be used, and the σp value of the soluble group is 0.4.
It is preferably 0 or more, more preferably 0.45
Or more, and more preferably 0.50 or more. However, when the soluble group has a σp value of 0.4 or more, the obtained phthalocyanine dye (including the phthalic acid derivative as a raw material)
Does not contain a sulfo group, or the sulfo group does not directly bond to the phthalocyanine nucleus (benzene ring structure: in the case of the phthalic acid derivative which is the raw material, the benzene ring structure) in the phthalocyanine dye. When it has a sulfo group, it must be bound to the phthalocyanine nucleus via a linking group.

When the resulting phthalocyanine dye has a plurality of substituents (including a soluble group) other than a hydrogen atom in the phthalocyanine nucleus (benzene ring structure) in the structure, the substituent (including a soluble group) is also included. ) Sum of σp values is 0.5
It is preferably 0 or more, and more preferably 0.55.
Or more, and more preferably 0.60 or more.

Here, the Hammett's substituent constant σp value will be briefly described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives in 1935 L.A. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σ
There are m-values and these values can be found in many common texts, for example J. A. Dean, "La
nge's Handbook of Chemist
ry ", 12th Edition, 1979 (McGraw-Hil
l) and "Chemical Area" special edition, No. 122, 96-103
Details on page 1979 (Nankodo).

Thus, as a result of introducing a substituent having a large electron-withdrawing property as a soluble group, a phthalocyanine dye having a high oxidation potential can be obtained, but the oxidation potential is 1.0 V (vs SCE). ) Is preferred. The higher the oxidation potential is, the more preferable, and the oxidation potential is more preferably higher than 1.1 V (vs SCE), and most preferably higher than 1.2 V (vs SCE).

The oxidation potential value (Eox) can be easily measured by those skilled in the art. For this method, see P. “New Instrument” by Delahay
talMethods in Electrochem
“Istry” (Interscience, 1954)
Published by Publishers) and A. J. "Electrochemical Methods" by Bard et al.
(Published by John Wiley & Sons in 1980),
Akira Fujishima et al., "Electrochemical measurement method" (published by Gihodo Publishing Co. in 1984).

The supporting electrolyte and solvent used in the measurement of the present invention can be appropriately selected depending on the oxidation potential and solubility of the test sample. The supporting electrolytes and solvents that can be used are described in Aki Fujishima et al., "Electrochemical Measurement Method" (1984, published by Gihodo Publishing Co., Ltd.), pages 101 to 118. In the present invention, the oxidation potential was measured by direct current polarography by dissolving a test sample in 1 × 10 ⁻⁴ to 1 × 10 ⁻⁶ mol / liter in dimethylformamide containing tetrapropylammonium perchlorate as a supporting electrolyte. It is measured as a value for a carbon (GC) electrode as a working electrode, a platinum electrode as a counter electrode, and an SCE (saturated calomel electrode) as a reference electrode. Although this value may deviate by about several tens of mil volts due to the influence of the liquid-potential difference and the liquid resistance of the sample solution, the reproducibility of the potential can be guaranteed by inserting a standard sample (for example, hydroquinone).

The conditions for synthesizing the phthalic acid derivative and the metal derivative in the method for producing the phthalocyanine dye of the present invention will be described in detail.

The molar ratio of the phthalic acid derivative to the metal derivative used is 3: (metal derivative: phthalic acid derivative).
1 to 6: 1 is preferred. The reaction between the phthalic acid derivative and the metal derivative is usually performed in the presence of a solvent. As the solvent, an organic solvent having a boiling point of 80 ° C. or higher, preferably 130 ° C. or higher is used. For example, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1
-Octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol, diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, urea and the like. The amount of the solvent used is 1 to 100 of the phthalic acid derivative.
It is preferably mass times, more preferably 5 to 20.
It is mass times. The reaction between the phthalic acid derivative and the metal derivative may be carried out in the presence of a catalyst. As a catalyst 1,
Examples thereof include 8-diazabicyclo [5.4.0] -7-undecene (DBU) and ammonium molybdate. The amount of the catalyst used is 1 mol of the phthalic acid derivative,
The molar amount is preferably 0.1 to 10 times, and more preferably 0.5 to 2 times.

The reaction between the phthalic acid derivative and the metal derivative is
It is preferably carried out in the reaction temperature range of 80 to 300 ° C, more preferably in the reaction temperature range of 100 to 250 ° C, and further preferably in the reaction temperature range of 130 to 230 ° C. If the reaction temperature is lower than 80 ° C, the reaction rate may be extremely slowed down, while if it exceeds 300 ° C, the phthalocyanine dye obtained may be decomposed. The reaction time is preferably 2 to 20 hours, more preferably 5 to 15 hours, and further preferably 5 to 10 hours. If the reaction time is less than 2 hours, a large amount of unreacted raw materials may exist, while if it exceeds 20 hours, the phthalocyanine dye obtained may be decomposed.

In the method for producing a phthalocyanine dye of the present invention, the product (phthalocyanine dye) obtained by these reactions is treated according to a usual post-treatment method for an organic synthesis reaction, and then purified or not purified. be able to. That is, for example, the product liberated from the reaction system is not purified, or is recrystallized or is subjected to column chromatography (eg, gel permeation chromatography (SEPHADEX ^™ LH-20: Pharmaci).
a) or the like and can be used by performing the purification operations individually or in combination.

After completion of the reaction, the reaction solvent is distilled off,
Alternatively, it may be poured into water or ice without being distilled off, and may be neutralized or the product released without being neutralized may not be purified, or may be solely purified by recrystallization, column chromatography, or the like, or It is also possible to offer after performing in combination. After completion of the reaction, the reaction solvent may be distilled off, or it may be poured into water or ice without distillation for neutralization, or the product extracted with an organic solvent / aqueous solution may be purified without purification. It is also possible to perform the purification without crystallization, or after the crystallization and the purification by column chromatography are carried out individually or in combination.

The phthalocyanine dye of the present invention can be used as a material for forming an image, particularly a color image. Specifically, a heat-sensitive transfer type image recording including a recording material (ink) for ink jet recording is used. Materials, pressure-sensitive recording materials, recording materials using electrophotography, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably inkjet recording recording materials (inks), heat-sensitive transfer image recording materials, A recording material using an electrophotographic method, and more preferably a recording material (ink) for inkjet recording. Also, US Pat. No. 4,808,501,
LC described in JP-A-6-35182
It can also be applied to color filters used in solid-state image pickup devices such as D and CCD, and dyeing solutions for dyeing various fibers. The phthalocyanine dye of the present invention is used by adjusting physical properties such as solubility and heat transfer property suitable for its use by a substituent.

[Inkjet Recording Ink, Inkjet Recording Ink Set] The inkjet recording ink of the present invention comprises the phthalocyanine dye of the present invention. The inkjet recording ink of the present invention has a good hue and is capable of forming an image having high fastness to active gas in the light and environment, particularly ozone gas,
High recording stability even when used under various environmental conditions.

The ink jet recording ink of the present invention comprises
Usually, it can be produced by dissolving and / or emulsifying and dispersing the phthalocyanine dye of the present invention in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used. 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, permeation accelerators, UV absorbers, preservatives, mildew-proofing agents, pH adjusting agents, surface tension adjusting agents. Known additives such as agents, defoamers, viscosity modifiers, dispersants, dispersion stabilizers, rust preventives and chelating agents can be mentioned. In the case of water-soluble ink, these various additives are added directly to the ink liquid. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after preparation of the dye dispersion, but it may be added to the oil phase or the water phase during the preparation.

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

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,
Polyhydric alcohols represented by dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane and the like; ethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-
Heterocycles such as 2-imidazolidinone and N-ethylmorpholine; sulfur-containing compounds such as sulfolane, dimethylsulfoxide and 3-sulfolene; polyfunctional compounds such as diacetone alcohol and diethanolamine; urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. It is preferable that the drying inhibitor is contained in the ink in an amount of 10 to 50% by mass. In conventional phthalocyanine dyes, when these water-soluble organic solvents are used, they act as poor solvents and only one or two sulfo groups described above are introduced, which are components having low solubility in the dye. A component that does not exist may deposit during long-term storage, causing clogging of the head and deteriorating the print image quality. However, since the phthalocyanine dye of the present invention has excellent solubility, such a problem can be overcome.

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

The ultraviolet absorber is used for the purpose of improving the storability of images. As the ultraviolet absorber, benzotriazole described in JP-A-58-185677, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057 and the like. Compounds, JP-A-46-2784, JP-A-5-194843, US Pat. No. 3,214,463
Compounds described in Japanese Patent Publication No. Sho-48
No. 30492, No. 56-21114, and the cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, and JP-A-8-53427.
JP-A-8-239368, JP-A-10-1826.
21, the triazine-based compounds described in JP-A-8-501291, Research Disclosure No. A compound which absorbs ultraviolet rays and fluoresces, which is represented by the compounds described in No. 24239 and stilbene compounds and benzoxazole compounds, that is, a so-called fluorescent brightening agent can also be used.

The anti-fading agent is used for the purpose of improving the storability of images. 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, indans, chromanes, alkoxyanilines, heterocycles, etc., and metal complexes include nickel. Complex, zinc complex and the like. More specifically, Research Disclosure No. 176
No. 43, Item VII, I to J, ibid. 15162, same N
o. 18716, page 650, left column, same No. 36544, page 527, ibid. 307105, page 872, ibid.
The compounds described in the patent cited in 15162 and the compounds included in the general formulas and the compound examples of the representative compounds described on pages 127 to 137 of JP-A No. 62-215272 can be used.

As a fungicide, sodium dehydroacetate,
Sodium benzoate, sodium pyridinethione-1-
Oxide, p-hydroxybenzoic acid ethyl ester,
1,2-benzisothiazolin-3-one and salts thereof and the like can be mentioned. These are 0.02-1.0 in the ink
It is preferable to use 0% by mass.

As the pH adjusting agent, the above neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the inkjet recording ink, the pH adjusting agent has a pH of 6% or less.
10 to 10 is preferably added for summer, and more preferably pH 7 to 10.

Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. The surface tension of the inkjet recording ink of the present invention is 25 to 7
0 mPa · s is preferable. Furthermore, 25-60 mN / m is preferable. The viscosity of the inkjet recording ink of the present invention is preferably 30 mPa · s or less. 20 mPa
-It is more preferable to adjust to s or less. Examples of surfactants include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates,
Anionic surfactants such as polyoxyethylene alkyl sulfate ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester,
Nonionic surfactants such as polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethyleneoxypropylene block copolymer are preferable. Also,
SURFYNOLS (AirProducts & C), an acetylene-based polyoxyethylene oxide surfactant
Chemicals) is also preferably used. Also,
Also preferred are amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide. Further, JP-A-59-157,636 (37) to (3)
8) page, Research Disclosure No. 3081
Those listed as the surfactants in 19 (1989) can also be used.

As the defoaming agent, a fluorine-based compound, a silicone-based compound, a chelating agent typified by EDTA, or the like can be used if necessary.

In the ink jet recording ink of the present invention, when a phthalocyanine dye is dispersed in an aqueous medium, JP-A No. 11-286637 and Japanese Patent Application No. 200 are used.
0-78491, 2000-80259, 20
As described in JP-A-00-62370, colored fine particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium, or Japanese Patent Application No.
000-78454, 2000-78491, 2000-203856, 2000-203857.
It is preferable to disperse a phthalocyanine dye dissolved in a high boiling point organic solvent in an aqueous medium as described in No. A specific method for dispersing a phthalocyanine dye in an aqueous medium,
As the oil-soluble polymer, the high-boiling point organic solvent, the additive, and the amount used thereof, those described in the above publications and the like can be preferably used. Regarding the method for preparing the ink jet recording ink, in addition to the above-mentioned patents, JP-A-5-148436, 5-295312 and 7
-97541, 7-82515, 7-1185.
84, Japanese Patent Laid-Open No. 11-286637, Japanese Patent Application No. 2
No. 000-87539, which can be used for preparing the ink jet recording ink of the invention.

As the aqueous medium, a mixture containing water as a main component and, if desired, a water-miscible organic solvent added thereto can be used. Examples of water-miscible organic solvents are alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols. Classes (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (for example, 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), amines (eg,
Ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (for example,
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) included. The water-miscible organic solvent may be used in combination of two or more kinds. In conventional phthalocyanine dyes, when these water-soluble organic solvents are used, they act as poor solvents and only one or two sulfo groups described above are introduced, which are components having low solubility in the dye. The non-existing component may deposit during long-term storage, causing clogging of the head and deteriorating the print image quality. However, the phthalocyanine dye of the present invention has excellent solubility, so that such a problem can be overcome.

The ink jet recording ink of the present invention comprises
It can be used for full-color image formation as well as single-color image formation. To form a full-color image,
Magenta tone ink, cyan tone ink, and yellow tone ink can be used. Further, by using these color tone inks in combination with the phthalocyanine dye of the present invention, a wide range of visible color tone can be obtained, and a black color tone ink may also be used. The dyes (dye, pigment, etc.) of each color applicable to these color tone inks are shown below.

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

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

Examples of applicable black materials include disazo, trisazo and tetraazo dyes, as well as carbon black dispersions. Each of the dyes may exhibit yellow and cyan colors only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium. However, it may be an organic cation such as a pyridinium or a quaternary ammonium salt, or a polymer cation having a partial structure thereof.

In the ink jet recording ink of the present invention, the phthalocyanine dye is preferably contained in an amount of 0.2 to 10 parts by mass based on 100 parts by mass of the ink jet recording ink.

The ink jet recording ink of the present invention comprises
Two or more kinds having different dye concentrations can be used as an inkjet recording ink set (the inkjet recording ink set of the present invention). In recent years, in order to obtain high image quality in the inkjet recording system,
In order to have different print densities for dyes of the same color, dark and light two-color inks or inks with three-stage dye density have been used as a set. Since the phthalocyanine dye has excellent solubility and excellent dissolution stability even when dissolved in a high concentration, it is particularly preferable to use it in these multi-stage concentration ink sets. Other dyes may be used in combination with the phthalocyanine dye. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

[Inkjet recording method] In the inkjet recording method of the present invention, energy is applied to the inkjet recording ink of the present invention to eject liquid droplets of the ink onto the image receiving material, thereby recording an image on the image receiving material. Is the way to do it.

An image receiving material for recording an image is a known image receiving material, that is, plain paper or resin coated paper, for example, JP-A-8-1.
No. 69172, No. 8-27693, No. 2-2
No. 76670, No. 7-276789, No. 9-
No. 323475, Japanese Patent Laid-Open No. 62-238783, Japanese Patent Laid-Open No. 10-153989, and Japanese Patent Laid-Open No. 10-217.
No. 473, No. 10-235995, No. 10-
Inkjet dedicated papers, films, electrophotographic co-papers, cloths, glass, metals, ceramics and the like described in 337947, 10-21797, 10-337947 and the like can be mentioned.

As the image receiving material, a polymer latex compound may be used for the purpose of imparting glossiness and water resistance and improving weather resistance when forming an image. The latex compound may be applied to the image receiving material before, after, or simultaneously with the application of the colorant. Therefore, even if it is added in the image receiving material,
It may be in the ink jet recording ink of the present invention, or may be used as a liquid substance of the polymer latex alone. Specifically, Japanese Patent Application No. 2000-3630
No. 90, No. 2000-315231, No. 2000-3
54380, 2000-343944, 200
The methods described in 0-268952, 2000-299465 and 2000-297365 can be preferably used.

As the image receiving material, a material having an ink receiving layer containing a white pigment on a support is particularly preferable from the viewpoint of being able to form an image with a good hue and high image quality. As the support, chemical pulp such as LBKP and NBKP, GP, PGW, RMP, TMP, CTM
P, CMP, CGP, etc. mechanical pulp, DIP, etc. waste paper pulp, etc., and if necessary, conventionally known additives such as pigments, binders, sizing agents, fixing agents, cation agents, paper strengthening agents, etc. are mixed. Those manufactured by various devices such as a fourdrinier paper machine and a cylinder paper machine can be used. In addition to these supports, synthetic paper or plastic film sheet may be used, and the support preferably has a thickness of 10 to 250 μm and a basis weight of 10 to 250 g / m ² . The support may be provided with the ink receiving layer and the back coat layer as it is, or may be provided with the ink receiving layer and the back coat layer after the size press or the anchor coat layer is provided with starch, polyvinyl alcohol or the like. Further, the support may be subjected to flattening treatment by a calendar device such as a machine calendar, a TG calendar and a soft calendar. As the support, a paper or plastic film having both surfaces laminated with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) is more preferably used. In the polyolefin, white pigments (eg titanium oxide, zinc oxide) or tinting dyes (eg cobalt blue,
Ultramarine blue, neodymium oxide) are preferably added.

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

As the aqueous binder, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose,
Examples thereof include water-soluble polymers such as polyvinylpyrrolidone, polyalkylene oxide and polyalkylene oxide derivatives, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. These aqueous binders can be used alone or in combination of two or more. In the present invention, among them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peeling resistance of the ink receiving layer. The ink receiving layer may contain a mordant, a water-proofing 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. Regarding the polymer mordant, JP-A-48-28325 and JP-A-54-74430 are used.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
0-23851, 60-2852, 60-2
3853, 60-57836, 60-6064.
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236.
Publications, US Pat. Nos. 2,484,430 and 25,485.
No. 64, No. 3148061, No. 3309690, No. 4115124, No. 4124386, No. 41938.
No. 00, No. 4273853, No. 4282305, and No. 4450224. JP-A-1-
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-161236 is particularly preferable. When the polymer mordant described in the publication is used, an image with excellent image quality can be obtained and the light resistance of the image can be improved.

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

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine type antioxidants, benzophenone type and benzotriazole type ultraviolet absorbers. Of these, zinc sulfate is particularly preferable.

The surfactant is a coating aid, a peelability improver,
Functions as a slipperiness improver or antistatic agent. The surfactant is described in JP-A-62-173463 and JP-A-62-183457. An organic fluoro compound may be used instead 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). Regarding organic fluoro compounds, Japanese Patent Publication No. 57-9
No. 053 (columns 8 to 17), JP-A-61-20994.
And No. 62-135826. Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners, preservatives,
Examples thereof include pH adjusters, matting agents, hardeners and the like. The ink receiving layer may be one layer or two layers.

The image-receiving material may be provided with a back coat layer, and components that can be added to this layer include a white pigment, an aqueous binder and other components. As the white pigment contained in the back coat layer, for example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide,
Zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide,
Alumina, lithopone, zeolite, hydrohaloysite,
Examples include white inorganic pigments such as magnesium carbonate and magnesium hydroxide, styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins, melamine resins and other organic pigments.

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

A polymer latex may be added to the constituent layers (including the back coat layer) of the image receiving material. The polymer latex is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film cracking prevention. Regarding the polymer latex, JP-A-62-1
No. 245258 and No. 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 or curling of the layer can be prevented. Curling can also be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink jet recording method of the present invention is not particularly limited, and known methods such as a charge control method for ejecting ink by utilizing electrostatic attraction and a drop-on-demand method (pressure for utilizing vibration pressure of a piezo element). Pulse method), change the electric signal into an acoustic beam and irradiate the ink,
It is used in an acoustic inkjet method in which ink is ejected by utilizing radiant pressure, a thermal inkjet method in which ink is heated to form bubbles, and the generated pressure is utilized. The inkjet recording method is a method of ejecting a large number of low density ink called photo ink in a small volume,
A method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a method of using colorless and transparent inks are included.

[Container] The container of the present invention is a container containing the ink for ink jet recording of the present invention, and examples thereof include a cartridge and a bottle which can be attached to an ink jet recording apparatus. Further, the ink jet recording apparatus in which the container of the present invention is attached to the ink tank portion has excellent solubility even when the phthalocyanine dye is stored in the container or the apparatus for a long period of time and exposed to various environmental conditions. Therefore, the problem of precipitation of a component having low solubility is less likely to occur.

[0106]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Hereinafter, the specific compounds 2, 3, 4, 5 will be described.
An example of the synthesis of [Synthesis Example 1] (Synthesis of Compound 2) Under nitrogen stream, 26.0 g of 4-nitrophthalonitrile was dissolved in 200 mL of DMSO (dimethyl sulfoxide), and the mixture was stirred at an internal temperature of 20 ° C for 30.
3 g of sodium 3-mercapto-propane-sulfonate was added, followed by the slow addition of 24.4 g of anhydrous sodium carbonate. Further, the reaction solution was heated to 80 ° C. with stirring and stirred at the same temperature for 1 hour. After that, cool to 20 ° C., filter the reaction solution with Nutsche, and collect the filtrate 1500 mL.
Was poured into ethyl acetate for crystallization, followed by stirring at room temperature for 30 minutes, and the precipitated crude crystals were filtered through a Nutsche, washed with ethyl acetate and dried. The crude crystals obtained are methanol /
Recrystallization from ethyl acetate gave compound E: 4- (3-sulfopropylsulphenyl) phthalonitrile Na salt 4
2.5 g was obtained.

42.0 g of Compound A was dissolved in 300 mL of acetic acid, and 2.5 g of Na ₂ W was added with stirring at an internal temperature of 20 ° C.
After adding O ₄ .2H ₂ O, the mixture was bathed in water and cooled to an internal temperature of 10 ° C. Subsequently, 32 mL of hydrogen peroxide solution (30%) was gradually added dropwise while paying attention to heat generation. Furthermore, the internal temperature is 15 to 2
After stirring at 0 ° C for 30 minutes, the reaction solution was heated to an internal temperature of 60 ° C and stirred at the same temperature for 1 hour. Then, cool to 20 ° C., inject 1500 mL of ethyl acetate into the reaction solution,
Subsequently, the mixture was stirred at the same temperature for 30 minutes, and the precipitated crude crystals were filtered with a Nutsche, washed with 200 mL of ethyl acetate and dried. The obtained crude crystals were purified by heating and washing with methanol / ethyl acetate, and compound F: 4- (3-sulfopropylsulfonyl) phthalonitrile Na salt 40.
0 g was obtained.

Under a nitrogen stream, 4-nitrophthalonitrile 2
After dissolving 6.0 g in 200 mL DMF (dimethylformamide), 29.3 g of 3-carboxybenzenesulfinic acid was added with stirring at an internal temperature of 20 ° C., and then 4
2 mL triethylamine was added slowly. Further, the reaction solution was heated to 80 ° C. with stirring and stirred at the same temperature for 1 hour. After that, it was cooled to 20 ° C. and the reaction solution was added with hydrochloric acid 35
Crystallization was performed by pouring the mixture into 1000 mL of water containing mL, and the precipitated crude crystals were filtered with a Nutsche, washed with water and dried. The obtained crude crystals were recrystallized from methanol / ethyl acetate to obtain 33.2 g of compound G: 4- (3-carboxyphenylsulfonyl) phthalonitrile.

70 mL of n-amyl alcohol was placed in a three-necked flask equipped with a cooling tube, and compound F5.0 was added thereto.
g, compound G 1.6 g, and copper chloride 1.0 g were added, and 7.0 mL of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) was added dropwise at room temperature with stirring. Subsequently, the reaction solution was heated to an internal temperature of 100 ° C. and stirred at the same temperature for 10 hours. Then cool to 40 ° C,
250 mL of heated methanol at 50 ° C. was added, and the mixture was stirred under reflux for 1 hour. Next, after cooling the reaction solution to room temperature, the obtained solid was filtered with a Nutsche and washed with 200 mL of methanol. Subsequently, the obtained solid was added to 100 mL of a 1 M aqueous hydrochloric acid solution saturated with sodium chloride,
Unreacted copper salt was dissolved. After filtering the insoluble matter, 300 mL of methanol was added dropwise to the filtrate for crystallization, and the obtained crude crystals were filtered with a Nutsche and washed with 200 mL of methanol. The crude crystal was dissolved in 50 mL of water, and 100 mL of a saturated methanol solution of sodium acetate was gradually added to the aqueous solution while stirring to form a salt. While further stirring, the mixture was heated to the reflux temperature and stirred at the same temperature for 1 hour. After cooling to room temperature, the precipitated crystals were filtered and washed with methanol. Continuously, 80% methanol 10
The obtained crystal was added to 0 mL, stirred under reflux for 1 hour, cooled to room temperature, and the precipitated crystal was filtered, and the obtained crystal was added to 100 mL of 70% methanol aqueous solution, stirred under reflux for 1 hour, and allowed to reach room temperature. After cooling, the precipitated crystals were filtered, washed with 100 mL of methanol and dried to give compound 2
3.2 g of blue crystals of The solubility of Compound 2 in water at 20 ° C. was 29% (W / V). (W / V represents the mass (g) of dye that can be dissolved in 1 mL of water.)

[Synthesis Example 2] (Synthesis of Compound 3) In the synthesis of Compound 2, the amounts of the synthesized Compounds F and G added to 70 mL of n-amyl alcohol were 3.4 g for Compound F and 3.2 g for Compound G.
Compound 3 was synthesized in the same manner as the synthesis of compound 2 except that the above was changed to. The solubility of compound 3 in water at 20 ° C. was 24% (W / V).

[Synthesis Example 3] (Synthesis of Compound 4) In the synthesis of Compound 2, the amounts of the synthesized Compounds F and G added to 70 mL of n-amyl alcohol were 1.7 g for Compound F and 4.8 g for Compound G.
Compound 4 was synthesized in the same manner as the synthesis of compound 2 except that the above was changed to. The solubility of Compound 4 in water at 20 ° C. was 21% (W / V).

[Synthesis Example 4] (Synthesis of Compound 5) In the synthesis of Compound 2, the addition amount of the synthesized Compounds F and G to 70 mL of n-amyl alcohol was 6.0 g for Compound F and 0.8 g for Compound G.
Compound 5 was synthesized in the same manner as the synthesis of compound 2 except that the above was changed to. The solubility of compound 5 in water at 20 ° C. was 32% (W / V).

Example 1 (Preparation of Aqueous Ink) The components below were stirred for 1 hour while heating at 30 to 40 ° C., and then pressure filtered using a microfilter having an average pore diameter of 0.8 μm and a diameter of 47 mm. Ink liquid A was prepared. —Composition of Ink Liquid A— Dye (Specific Compound Example 2) 5 parts by mass Diethylene glycol 9 parts by mass Tetraethylene glycol monobutyl ether 9 parts by mass Glycerin 7 parts by mass Diethanolamine 1 part by mass Water 70 parts by mass

Ink liquids B to K were prepared in the same manner as the ink liquid A except that the azo dye was changed as shown in Table 7 below.

The following samples were used as comparative examples. Comparative Dye 1: Compound Dye 2 of Synthesis Example 2 of JP-A-2000-30009: C.I. I. Direct Blue 86 Comparative Dye 3: C.I. I. Direct Blue 87 Comparative Dye 4: C.I. I. Direct Blue 199

(Image recording and evaluation) Using the ink liquids A to I, an ink jet printer (PM-700C, manufactured by Seiko Epson Corporation) was used to produce photo gloss paper (Fuji Photo Film Co., Ltd. inkjet paper, Super Photo). The image was recorded on the grade). The hue and light fastness of the obtained image were evaluated.

<Hue> The hue was visually evaluated according to the following criteria. [Criteria] ◯: The hue is the best Δ: Good X: It is defective.

<Light fastness> Image density Ci immediately after recording
After measuring, the weather meter (Atlas C.16
5) was used to irradiate the image with xenon light (85,000 lux) for 7 days, and then the image density Cf was measured again, and the dye residual ratio ({(Ci
−Cf) / Ci} × 100%) was calculated and evaluated according to the following criteria. Image density is measured by reflection densitometer (X-Rite310T
R).

[Criteria for Judgment] The reflection density was measured at three points of 1, 1.5 and 2.0. ◯: The dye residual rate is 90% or more at any concentration. Δ: The residual dye ratio is less than 90% at the density of 2 points. X: The dye residual rate is less than 90% at any concentration.

<Ozone gas resistance> The image immediately after recording is left for 72 hours in a box in which the ozone gas concentration is set to 0.5 ppm, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X-Rite 310TR). The residual amount of the dye was evaluated according to the following criteria. The ozone gas concentration in the box was set using an ozone gas monitor manufactured by APPLICS (model: OZG-EM-01).

[Criteria for Judgment] The reflection density was measured at three points of 1, 1.5 and 2.0. ◯: The residual dye rate is 70% or more at any concentration. Δ: The residual dye ratio is less than 70% at a concentration of 1 or 2 points. X: The residual dye ratio is less than 70% at any concentration.

<Ink Storage Stability> The solubility of the dye was evaluated by conducting a storage stability test and a clogging recovery test on the ink. Ink storage stability is determined by placing the ink liquids A to K in a polyethylene container at -20 ° C and
It was stored under the condition of 70 ° C. for 3 months, and the presence or absence of insoluble matter precipitation before and after storage was examined and evaluated according to the following criteria.

[Judgment Criteria] The recording liquid after aging was put in a test tube and visually observed. ◯: Insoluble matter is not observed at all. Δ: A small amount of insoluble matter was observed. X: Insoluble matter is conspicuous and not in a practical level.

<Recovery from clogging> The printer is filled with each ink and left in an environment of 40 ° C. for 1 month without a cap. The following criteria were evaluated.

[Criteria] A: Return within 2 cleanings. B: Return after 3 to 5 cleanings. C: Return after 6 or more cleanings. NG: Does not return.

<Solubility> Solubility is the solubility (%) of the compound in water at 20 ° C., and W / V represents the mass (g) of dye that can be dissolved in 1 mL of water.

[0128]

[Table 7]

As shown in Table 7, the cyan images obtained from the ink liquids A to G have higher fastness than the cyan images obtained from the ink liquids H to K, and in particular, there is a remarkable difference in ozone gas resistance. Was recognized. Further, it was found that the ink liquid prepared by the preparation method of the present invention did not deteriorate the printing due to the precipitation of the low-soluble component even when exposed to severe storage conditions, and was excellent in the ink storage stability and the clogging recovery property.

Example 2 (Preparation of Sample 201) Cyan Dye (Specific Compound Example 4)
3; oil-soluble dye) (4.83 g) and sodium dioctylsulfosuccinate (7.04 g) were added to the following high boiling organic solvent (s-
2) 4.22 g, the following high boiling point organic solvent (s-11) 5.
Dissolved in 63 g and 50 ml of ethyl acetate at 70 ° C. To this solution, 500 ml of deionized water was added while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion was passed through a microfluidizer (MICROFLUIDEX INC) at a pressure of 600 bar (60 MPa) five times to make fine particles. The resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. A fine emulsion of the hydrophobic dye thus obtained was added to 140 g of diethylene glycol, 50 g of glycerin, SURFYNOL465 (AirProd
cts & Chemicals) 7 g, deionized water 9
An ink was prepared by adding 00 ml.

[0131]

[Chemical 4]

(Production of Samples 202 to 204) Sample 201
Except that the cyan dye (Specific Compound Example 43; oil-soluble dye) in Example 2 was changed to the cyan dye (oil-soluble dye) in Table 8 below.
Samples 202 to 204 were prepared in the same manner as the sample 201.

Comparative Dye 5 was prepared by deriving a copper phthalocyanine tetrasulfonyl chloride from copper phthalocyanine according to the method described in WO 00/08103 and then reacting it with 4-octylaniline.

With respect to the samples 201 to 204 thus obtained and the comparative sample, the volume average particle size of the emulsion-dispersed ink was measured using Microtrac UPA (Nikkiso Co., Ltd.). Further, the following evaluations were performed on the ink samples 201 to 204 and the comparative sample. In addition, "color tone" and "light resistance" refer to each inkjet ink as an inkjet printer (manufactured by EPSON Corporation; PM-700C).
It was evaluated after recording an image on a photo glossy paper (Fuji Photo Film Co., Ltd .; inkjet paper, photo grade).

<Hue> 390 to 730n of recorded image
A reflection spectrum at an interval of 10 nm in the m region was measured, and a ^* and b ^* were calculated based on the CIE L ^* a ^* b ^* color space system. The color tone preferable for magenta is defined as follows.

[Criteria] Preferable a ^* : 76 or more, preferable b ^* : -30 or more and 0 or less A: a ^* and b ^* are both preferable regions B: a ^* and b ^* are preferable region C: a ^* , None of b ^* is outside the preferred range

<Light fastness> Xenon light (85000 lx) was irradiated to the photo glossy paper on which the image was formed by using a weather meter (Atlas CI65) for 10 days, and the image density before and after the xenon irradiation was measured as a reflection density. Total (X-R
(ite 310TR), and the dye residual rate was evaluated according to the following criteria.

[Criteria] The reflection density was measured at three points of 1, 1.5 and 2.0. A: The residual dye ratio is 80% or more at any concentration. B: 1 or 2 points is less than 80%. C: The residual dye ratio is less than 80% at any concentration.

<Ozone gas resistance> The photo glossy paper on which the image is formed is left to stand in a box in which the ozone gas concentration is set to 0.5 ppm for 24 hours, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X- Rite310TR)
Was measured, and the residual rate of the dye was evaluated according to the following criteria. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box is APPL
ICS ozone gas monitor (model: OZG-EM-
01).

[Judgment Criteria] A: The residual dye ratio is 70% or more at any concentration. B: 1 or 2 points is less than 70%. C: The dye residual rate is less than 70% or more at any concentration.

<Ink Storage Stability and Clog Recovery> In the same manner as in Example 1, each ink was tested for storage stability and clog recovery to evaluate the solubility of the dye.

[0142]

[Table 8]

As is clear from Table 8, the ink jet ink of the present invention was excellent in color tone, fastness against light and ozone gas, ink storage stability, and clogging recovery.

[Example 3] The same ink prepared in Example 2 was used as an ink jet printer BJ-F850 (CA).
Example 2 in which the image is printed on the photo glossy paper GP-301 of the same company.
The same evaluation as in Example 2 was performed, and the same results as in Example 2 were obtained.

[0145]

EFFECTS OF THE INVENTION According to the present invention, 1) As a dye of three primary colors, it has excellent absorption characteristics with excellent color reproducibility and has sufficient fastness to light, heat, humidity and active gas in the environment. A method for producing a novel phthalocyanine dye having excellent solubility,
And a coloring composition using the phthalocyanine dye obtained by the production method, and 2) the use of the coloring composition has excellent ink storage stability and clogging recovery, and has a good hue. Inks, inkjet recording inks, inkjet recordings that can form images with high robustness against light and active gas in the environment, especially ozone gas, and have high recording stability even when used under various environmental conditions. It is possible to provide an ink set for use, an inkjet recording method using the inkjet recording ink, and a container.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09B 47/073 C09B 47/08 47/08 67/20 G 67/20 C09D 11/00 C09D 11/00 B41J 3/04 101Y (72) Inventor Masaki Noro 210 Nakanuma, Minamiashigara City, Kanagawa Fuji Photo Film Co., Ltd. F-term (reference) 2C056 EA13 FC02 2H086 BA02 BA51 BA55 4C050 PA12 PA13 PA15 4C072 BB04 CC04 CC13 EE09 FF16 GG01 HH02 4J039 BC GA24

Claims (9)

[Claims] 1. A phthalocyanine obtained by reacting at least two kinds selected from a phthalonitrile having a different soluble group or a precursor thereof and a phthalic acid derivative having a different soluble group or a precursor thereof with a metal derivative. A method for producing a phthalocyanine dye, which comprises producing a dye. 2. The phthalocyanine dye comprises a phthalocyanine skeleton having four benzene rings, and the four benzene rings have different solubility groups having a Hammett's substituent constant σp value of 0.4 or more. 2. The method for producing a phthalocyanine dye according to claim 1, wherein at least one of each is present. 3. A phthalocyanine dye obtained by the method for producing a phthalocyanine dye according to claim 1. 4. A coloring composition comprising the phthalocyanine dye according to claim 3. 5. An ink containing the coloring composition according to claim 4. 6. An ink jet recording ink containing the coloring composition according to claim 4. 7. An ink jet recording ink set comprising two or more types of ink jet recording inks having different dye concentrations, wherein the ink jet recording ink comprises:
An inkjet recording ink set comprising the inkjet ink according to claim 6. 8. An ink jet recording method, characterized in that energy is applied to the ink for ink jet recording according to claim 6 to eject droplets of the ink onto an image receiving material to record an image on the surface of the image receiving material. . 9. A container containing the ink for ink jet recording according to claim 6.