JP6037991B2 - Ink set, textile printing method, and fabric - Google Patents

Description

  The present invention relates to an ink set, a textile printing method, and a fabric.

For example, when forming an image on a fabric mainly composed of polyamide fibers such as silk, wool and nylon, a method using an acid dye has been known for a long time, and many methods using a phthalocyanine acid dye as an acid dye are also employed. ing.
Specifically, for example, Patent Document 1 discloses an ink for ink jet textile printing containing an acid dye including a phthalocyanine acid dye, water, and ethylene glycol.

  On the other hand, as an ink composition using a phthalocyanine-based dye, for example, in patent literature, a dye having an acidic group of sulfonic acid, carboxylic acid, or phenol group, and a quaternary ammonium ion as a counter ion of the acidic group of the dye A water-based ink composition for inkjet recording is disclosed.

JP 2004-292522 A Japanese Patent Publication No. 2-3827

The conventionally proposed phthalocyanine dye has a slower dyeing speed than other dyes that do not have a phthalocyanine skeleton in order to obtain a desired dyeing density when dyeing a fabric mainly composed of polyamide fibers such as nylon. If the dyeing time is long or the dyeing time is short, the dyeing density is lowered.
Therefore, in the case of an ink set including the ink composition using the above phthalocyanine dye and another ink composition using another dye having no phthalocyanine skeleton, a desired dyeing density between the two ink compositions As a result, there is a problem that when the dyeing time is made constant, the balance of the color becomes worse when the time for obtaining the color changes. On the other hand, in the case of such an ink set, if the dyeing time is increased in order to obtain a desired dyeing density, there is a concern that the manufacturing cost increases.
From the above, the present situation is that an ink set having an excellent balance of dyeing property among ink compositions is required.

This invention is made | formed in view of the above situations, and makes it a subject to achieve the following objective. That is,
An object of the present invention is to provide an ink set which is used for printing a fabric containing polyamide-based fibers and has an excellent balance of dyeing property between ink compositions.
Another object of the present invention is to provide a printing method capable of performing printing with excellent color balance and a fabric having a dyed image with excellent color balance.

In the present invention, by using an ink composition in which a phthalocyanine dye and a specific quaternary ammonium ion or pyridinium ion coexist, the dyeing property of the ink composition is specifically improved, and there is no phthalocyanine skeleton. The present inventors have obtained knowledge that the poor balance of dyeing property with other ink compositions using the above dyes has been improved, and have been achieved based on such knowledge.
Specific means for achieving the above-described problems are as follows.

<1>
A first ink composition comprising a phthalocyanine acid dye having a phthalocyanine skeleton, at least one ion selected from the group consisting of structures represented by the following general formulas (1) to (4), and water;
A second ink composition comprising a dye having a skeleton other than the phthalocyanine skeleton, and water;
An ink set used for printing a fabric containing at least polyamide-based fibers.

[In General Formula (1), R ^{11 to} R ¹⁴ are each independently a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or a tertiary alkyl group having 4 to 6 carbon atoms. Represents a group, and any two of R ^{11 to} R ¹⁴ may be bonded to each other to form a ring.
In General Formula (2), R ^{21 to} R ²⁵ are each independently a hydrogen atom, a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or 3 having 4 to 6 carbon atoms. Represents a secondary alkyl group, and any two of R ^{21 to} R ²⁵ may be bonded to each other to form a ring; R ²⁶ represents a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or a tertiary alkyl group having 4 to 6 carbon atoms.
In General Formula (3), R ^{31 to} R ³³ are each independently a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or a tertiary alkyl group having 4 to 6 carbon atoms. And any two of R ^{31 to} R ³³ may be bonded to each other to form a ring. L ¹ represents an alkylene group, —O—, —S—, —NR ³⁴ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ³⁵ —, —CONR ³⁶ —, —SiR ³⁷ ₂ —. , An arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these groups. Here, R ^{34 to} R ³⁷ each independently represents a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 3 to 20 carbon atoms, or a tertiary alkyl group having 4 to 20 carbon atoms.
In General Formula (4), R ^{41 to} R ⁴⁵ are each independently a hydrogen atom, a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or 3 having 4 to 6 carbon atoms. Represents a secondary alkyl group, and any two of R ^{41 to} R ⁴⁵ may be bonded to each other to form a ring. L ² represents an alkylene group, —O—, —S—, —NR ⁴⁶ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ⁴⁷ —, —CONR ⁴⁸ —, —SiR ⁴⁹ ₂ —. , An arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these groups. Here, R ^{46 to} R ⁴⁹ each independently represent a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 3 to 20 carbon atoms, or a tertiary alkyl group having 4 to 20 carbon atoms. ]

<2>
The ink set according to <1>, wherein the phthalocyanine acid dye in the first ink composition is a compound represented by the following general formula (P1) or (P2).

[In General Formula (P1), X ^{1 to} X ⁴ each independently represents an oxygen atom or a sulfur atom. R ^{1 to} R ⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. P ^{1 to} P ⁴ each independently represents an aromatic ring, and the aromatic ring is a halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, alkyl Oxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfo group Sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl Group, Sill group, an ionic hydrophilic group, a cyano group, a hydroxy group, a nitro group, an amino group, which may have a carbonyl group, and a substituent selected from carbonylamino group. n ¹ to n ⁴ each independently represents an integer of 0 to 4, and the sum of n ^{1 to} n ⁴ is at least 1. However, the structure of the general formula (P1) includes at least two ionic hydrophilic groups.
In General Formula (P2), Y ^{101 to} Y ¹¹² each independently represent —CH— or a nitrogen atom. ^However, the number of nitrogen atoms in each group of ^{Y 101 ~Y 104, Y 105 ~Y} 108, and ^Y 109 ^{to Y 112} is an integer of 0-2. R ¹⁰¹ represents a hydrogen atom, an oxygen radical (—O ·), a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and R ¹⁰² and R ¹⁰³ are each independently a carbon atom. A secondary alkyl group having 3 to 20 carbon atoms or a tertiary alkyl group having 4 to 20 carbon atoms is represented. Further, any one of R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring. L ¹⁰¹ represents an alkylene group, —O—, —S—, —NR ²⁰¹ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ²⁰¹ —, —CONR ²⁰¹ —, —SiR ²⁰¹ ₂ —. , An arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these groups. R ²⁰¹ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. One bond of L ¹⁰¹ is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, and the other bond is tetraaza It is bonded to the tetraazaporphyrin skeleton at the position where either the α-position or β-position hydrogen atom of the 6-membered ring of the porphyrin skeleton is removed. SO ₃ M ¹⁰² is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, or is a 6-membered ring of a tetraazaporphyrin skeleton. It is bonded to the tetraazaporphyrin skeleton at a position where either the α-position or β-position hydrogen atom is removed . M ¹⁰¹ represents a copper atom, a zinc atom, a nickel atom, or a cobalt atom, and M ¹⁰² represents a hydrogen atom or a monovalent counter cation. n ¹⁰¹ and n ¹⁰³ each independently represent an integer of 1 or more. ]

<3>
The dye having a skeleton other than the phthalocyanine skeleton in the second ink composition is an aryl or heteryl azo dye, azomethine dye, methine dye, quinone dye, quinophthalone dye, nitro dye, nitroso dye, acridine dye, acridinone dye, carbonium dye , polymethine dyes, Lee Njigo dye, and an ink set according to at least one dye selected from the group consisting of a thioindigo dye <1> or <2>.

<4>
The dye having a skeleton other than the phthalocyanine skeleton in the second ink composition is at least one dye selected from the group consisting of compounds represented by the following general formulas (D1) to (D6) <1> The ink set according to any one of to <3>.

[In General Formulas (D1) and (D2), A, B, and C each independently represent an aromatic group or a heterocyclic group. N is an integer of 1 or more. However, at least one — (SO ₃ M) is introduced into the aromatic group or heterocyclic group represented by A, B, and C. M represents a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ .
In General Formula (D3), R ^{301 to} R ³⁰⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. The R ³⁰⁵ to R ³¹⁷ each independently represent a group on the benzene ring, represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, or a phenoxy ^{group, R} 305 to R Any two of ³¹⁷ may be connected to form a ring. However, at least one of R ^{301 to} R ³¹⁷ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m1 represents an integer of 1 to 13.
In General Formula (D4), R ^{401 to} R ⁴⁰⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. R ^{405 to} R ⁴¹⁵ each independently represent a group on the benzene ring, and may be a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, aryl group, heteroaryl group, alkoxy group, amino group, or phenoxy. Represents a group, and any two of R ^{405 to} R ⁴¹⁵ may be linked to form a ring. However, at least one of R ^{405 to} R ⁴¹⁵ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m2 represents an integer of 1 to 11.
In general formula (D5), R ^{501 to} R ⁵⁰⁶ each independently represents a group on the benzene ring, and are a hydrogen atom, a hydroxy group, an alkyl group that may have a substituent, an aryl group, a heteroaryl group, An alkoxy group, an amino group, or a phenoxy group is represented, and X ¹ and X ² each independently represent —NR ⁵⁰⁷ R ⁵⁰⁸ , —OR ⁵⁰⁹ , or a hydroxy group. Any ^two of R ^{501 to} R ⁵⁰⁶ , X ¹ and X ² may be linked to form a ring. However, at least one of R ^{501 to} R ⁵⁰⁶ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m3 represents an integer of 1 to 6. R ⁵⁰⁷ , R ⁵⁰⁸ , and R ⁵⁰⁹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
In General Formula (D6), R ⁶⁰¹ and R ⁶⁰² each independently represent an alkyl group, an aryl group, or a heteroaryl group. R ^{603 to} R ⁶⁰⁹ each independently represents a group on the benzene ring, and represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, or a phenoxy group, and R ^{603 to} R ⁶⁰³ Any two of ⁶⁰⁶ and any two of R ^{607 to} R ⁶⁰⁹ may be linked to form a ring. However, at least one of R ^{601 to} R ⁶⁰⁹ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m4 represents an integer of 1 to 7. ]

<5>
<1>-<4> The printing method which dye | stains the cloth containing a polyamide fiber by the inkjet method using the ink set of any one of <4>.

<6>
A fabric printed with the ink set according to any one of <1> to <4>.

ADVANTAGE OF THE INVENTION According to this invention, the ink set used for the printing of the fabric containing a polyamide-type fiber and excellent in the dyeing | staining property between ink compositions is provided.
Further, according to the present invention, there are provided a printing method capable of performing printing with excellent color balance, and a fabric having a dyed image with excellent color balance.

  Hereinafter, the ink set of the present invention, the printing method of the present invention using the ink set, and the fabric will be described in detail.

<Ink set>
The ink set of the present invention includes a phthalocyanine dye having a phthalocyanine skeleton, at least one ion selected from the group consisting of structures represented by general formulas (1) to (4) described later, and water. An ink composition of
A second ink composition comprising a dye having a skeleton other than the phthalocyanine skeleton, and water;
Is used for printing of a fabric containing at least polyamide-based fibers.

In the present invention, in the first ink composition, a phthalocyanine dye having a phthalocyanine skeleton, and at least one ion selected from the group consisting of structures represented by the general formulas (1) to (4), It is characterized by coexisting.
By combining such a first ink composition with a second ink composition containing a dye having a skeleton other than the phthalocyanine skeleton to form an ink set, an ink set having an excellent balance of dyeing properties is formed. The

The reason why such an effect is obtained is not clear, but the following can be considered.
Conventionally proposed phthalocyanine dyes have a large molecular weight, a structure that easily associates, and the apparent molecular weight is further increased by association, so that it is difficult to enter the fibers of the fabric and the dyeing speed is slow. .
On the other hand, dyes having a skeleton other than the phthalocyanine skeleton tend to have a higher dyeing speed than phthalocyanine dyes due to their relatively low molecular weight and the like compared to phthalocyanine dyes.
In the case of an ink set in which ink compositions each containing dyes having different dyeing speeds are combined, the time for obtaining a desired dyeing density varies between the two ink compositions, and the dyeing time is constant. When this is done, the color balance will deteriorate. There is also a concern that the manufacturing cost increases if the dyeing time is increased in order to obtain a desired dyeing concentration.

In response to such a problem, the present inventors include a specific quaternary ammonium ion or pyridinium ion in the first ink composition containing a phthalocyanine dye, thereby dyeing the first ink composition. The knowledge that the sex improved specifically was acquired.
The reason for the improvement of the dyeing property is not clear, but the following phenomenon is captured.
That is, when an ink composition in which a phthalocyanine dye and a specific quaternary ammonium ion or pyridinium ion coexist is applied to a fabric, the phenomenon that the dye is localized and fixed near the surface of the fabric is captured. ing. As a result of the presence of a large amount of dye on the surface in this way, more dye is dyed inside the fiber in the subsequent steam process, and it is assumed that excellent dyeing properties are to be exhibited. Is done.
The specific quaternary ammonium ion or pyridinium ion used in the present invention is more hydrophobic than metal ions such as sodium ion, and is therefore easily adsorbed to the hydrophobic portion of the fabric including the polyamide fiber that is the object to be dyed. . And by adsorbing the adsorbed specific quaternary ammonium ion or pyridinium ion and the dye (anionic dye) electrostatically, it becomes easy for the dye to approach and adsorb to the surface of the object to be dyed, and the adsorption efficiency can be increased. It is thought that it contributes to the localization and fixation of such dyes.

As described above, the time required to obtain a desired dyeing density with the second ink composition containing a dye having a skeleton other than the phthalocyanine skeleton by increasing the dyeing property of the first ink composition. It is considered that an ink set having an excellent balance of dyeing property can be obtained as a result.
In the printing of nylon, which is a polyamide-based fiber, it is often performed under acidic conditions, and under this condition, the addition of a specific quaternary ammonium ion or pyridinium ion generally adversely affects the solubility of the dye, It is also conceivable that the dyeing performance is lowered. However, although the detailed action is unknown in the present invention, it is also characterized in that excellent dyeing properties can be obtained in spite of using a specific quaternary ammonium ion or pyridinium ion.

  Hereinafter, the first ink composition and the second ink composition constituting the ink set of the present invention will be described in order.

[First ink composition]
The first ink composition comprises at least one selected from the group consisting of (A-1) a phthalocyanine dye having a phthalocyanine skeleton and (B) a structure represented by the general formulas (1) to (4). It contains ions and (C) water, and may further contain other components as necessary.

[(B) Ions represented by general formulas (1) to (4)]
In the present invention, the first ink composition contains (B) at least one ion selected from the group consisting of structures represented by the following general formulas (1) to (4). .
Hereinafter, the ions represented by the general formulas (1) to (4) will be collectively referred to as “(B) specific ions” as appropriate.
First, ions represented by the following general formula (1) will be described. The ion represented by the following general formula (1) is a quaternary ammonium ion.

In the general formula (1), R ^{11 to} R ¹⁴ are each independently a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 1 to 20 carbon atoms, or a tertiary alkyl group having 1 to 20 carbon atoms. Represents a group, and any two of R ^{11 to} R ¹⁴ may be bonded to each other to form a ring.
Among the primary alkyl groups having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ , primary alkyl groups having 1 to 12 carbon atoms are preferable, and primary alkyl groups having 1 to 6 carbon atoms are more preferable. Specifically, an ethyl group, a butyl group, a heptyl group, a decyl group, a 2-ethylhexyl group, and the like can be given.
Among the secondary alkyl groups having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ , secondary alkyl groups having 1 to 12 carbon atoms are preferable, and secondary alkyl groups having 1 to 6 carbon atoms are more preferable. Specifically, an isopropyl group and the like can be mentioned.
Among the tertiary alkyl groups having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ , tertiary alkyl groups having 1 to 12 carbon atoms are preferable, and tertiary alkyl groups having 1 to 6 carbon atoms are more preferable. Specifically, t-butyl group, t-amyl group and the like can be mentioned.
Among these, R ^{11 to} R ¹⁴ are preferably primary alkyl groups.
In the general formula (1), R ^{11 to} R ¹⁴ each preferably has a structure in which the same alkyl group is introduced.

The alkyl group described above may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (specifically, Cl, Br, F, etc.), an aryl group (specifically, , Phenyl group, naphthyl group, etc.).
In addition, it is preferable that the alkyl group represented by R < ¹¹ > -R < ¹⁴ > is unsubstituted.

  Specific examples of the ions represented by the general formula (1) are shown below, but the present invention is not limited to these.

  Next, the ion represented by the following general formula (2) will be described. The ion represented by the following general formula (2) is a pyridinium ion.

In the general formula (2), R ^{21 to} R ²⁵ are each independently a hydrogen atom, a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 1 to 20 carbon atoms, or a carbon number having 1 to 20 carbon atoms. A tertiary alkyl group may be represented, and any two of R ^{21 to} R ²⁵ may be bonded to each other to form a ring.
Among the primary alkyl groups having 1 to 20 carbon atoms represented by R ^{21 to} R ²⁵ , primary alkyl groups having 1 to 12 carbon atoms are preferable, and primary alkyl groups having 1 to 6 carbon atoms are more preferable. Specifically, an ethyl group, a butyl group, a heptyl group, a decyl group, a 2-ethylhexyl group, and the like can be given.
Among the secondary alkyl groups having 1 to 20 carbon atoms represented by R ^{21 to} R ²⁵ , secondary alkyl groups having 1 to 12 carbon atoms are preferable, and secondary alkyl groups having 1 to 6 carbon atoms are more preferable. Specifically, an isopropyl group and the like can be mentioned.
Among the tertiary alkyl groups having 1 to 20 carbon atoms represented by R ^{21 to} R ²⁵ , a tertiary alkyl group having 1 to 12 carbon atoms is preferable, and a tertiary alkyl group having 1 to 6 carbon atoms is more preferable. Specifically, t-butyl group, t-amyl group and the like can be mentioned.
Among these, R ^{21 to} R ²⁵ are preferably each independently a hydrogen atom or a primary alkyl group (specifically, a methyl group or the like).

In the general formula (2), R ²⁶ represents a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 1 to 20 carbon atoms, or a tertiary alkyl group having 1 to 20 carbon atoms. These primary alkyl groups, secondary alkyl groups, and tertiary alkyl groups have the same preferred examples as the primary alkyl groups, secondary alkyl groups, and tertiary alkyl groups represented by R ^{21 to} R ^25. .
Among these, R ²⁶ is preferably a primary alkyl group (specifically, a methyl group, an ethyl group, a butyl group, etc.).

The alkyl group described above may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (specifically, Cl, Br, F, etc.), an aryl group (specifically, , Phenyl group, naphthyl group, etc.).
^The alkyl group represented by R 21 ^{to R 26} is preferably unsubstituted.

  Specific examples of the ions represented by the general formula (2) are shown below, but the present invention is not limited to these.

  Subsequently, an ion represented by the following general formula (3) will be described. The ion represented by the following general formula (3) is a quaternary ammonium ion.

In the general formula (3), R ^{31 to} R ³³ are each independently a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 1 to 20 carbon atoms, or a tertiary alkyl group having 1 to 20 carbon atoms. Represents a group, and any two of R ^{31 to} R ³³ may be bonded to each other to form a ring.
The primary alkyl group, secondary alkyl group, and tertiary alkyl group represented by R ^{31 to} R ³³ are the primary alkyl group and secondary alkyl represented by R ^{11 to} R ¹⁴ in the general formula (1). It is synonymous with a group and a tertiary alkyl group, and a preferable example is also the same.

In the general formula (3), L ¹ represents an alkylene group, —O—, —S—, —NR ³⁴ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ³⁵ —, —CONR. ^{36 -, - SiR 37 2 -} , an arylene group, a divalent heterocyclic group, and a divalent linking group selected from the divalent group formed by combining at least two of these. Here, R ^{34 to} R ³⁷ each independently represent a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 1 to 20 carbon atoms, or a tertiary alkyl group having 1 to 20 carbon atoms. The primary alkyl group, secondary alkyl group, and tertiary alkyl group represented by R ^{34 to} R ³⁷ are the primary alkyl group and secondary alkyl group represented by R ^{11 to} R ¹⁴ in the general formula (1). It is synonymous with a group and a tertiary alkyl group, and a preferable example is also the same.
L ¹ is preferably an alkylene group, more preferably an alkylene group having 1 to 12 carbon atoms, from the viewpoint of affinity with the hydrophobic portion of a fabric such as nylon, and the alkylene group may be unsubstituted. preferable.

The alkyl group described above may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (specifically, Cl, Br, F, etc.), an aryl group (specifically, , Phenyl group, naphthyl group, etc.).
^The alkyl group represented by R 31 ^{to R 33} is preferably unsubstituted.

  Specific examples of the ions represented by the general formula (3) are shown below, but the present invention is not limited to these.

  Subsequently, ions represented by the following general formula (4) will be described. The ion represented by the following general formula (4) is a pyridinium ion.

In the general formula (4), R ^{41 to} R ⁴⁵ are each independently a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 1 to 20 carbon atoms, or a tertiary alkyl group having 1 to 20 carbon atoms. Represents a group, and any two of R ^{41 to} R ⁴⁵ may be bonded to each other to form a ring.
The primary alkyl group, secondary alkyl group, and tertiary alkyl group represented by R ^{41 to} R ⁴⁵ are the primary alkyl group and secondary alkyl group represented by R ^{21 to} R ²⁵ in the general formula (2). It is synonymous with a group and a tertiary alkyl group, and a preferable example is also the same.

In the general formula (3), L ² represents an alkylene group, —O—, —S—, —NR ⁴⁶ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ⁴⁷ —, —CONR. ^{48 -, - SiR 49 2 -} , an arylene group, a divalent heterocyclic group, and a divalent linking group selected from the divalent group formed by combining at least two of these. Here, R ^{46 to} R ⁴⁹ each independently represent a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 1 to 20 carbon atoms, or a tertiary alkyl group having 1 to 20 carbon atoms. The primary alkyl group, secondary alkyl group, and tertiary alkyl group represented by R ^{46 to} R ⁴⁹ are the primary alkyl group and secondary alkyl group represented by R ^{11 to} R ¹⁴ in the general formula (1). It is synonymous with a group and a tertiary alkyl group, and a preferable example is also the same.
L ² is preferably an alkylene group, more preferably an alkylene group having 1 to 12 carbon atoms, from the viewpoint of affinity with a hydrophobic part of a fabric such as nylon, and the alkylene group is unsubstituted. Is preferred.

  The alkyl group described above may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (specifically, Cl, Br, F, etc.), an aryl group (specifically, , Phenyl group, naphthyl group, etc.).

  Specific examples of the ions represented by the general formula (4) are shown below, but the present invention is not limited to these.

(B) The ions (specific ions) represented by the general formulas (1) to (4) have (A-1) a phthalocyanine skeleton in the first ink composition in order to obtain the effects of the present invention. It only has to coexist with a phthalocyanine dye.
In order to make this coexist, if the (A-1) phthalocyanine dye having a phthalocyanine skeleton, which will be described later, is a dye having (B) a specific ion as a counter ion, the first ink composition is formed using such a dye. What is necessary is just to prepare.
As another method, (B) a method of preparing a first ink composition using a salt of a specific ion and a counter ion other than a phthalocyanine dye together with (A-1) a phthalocyanine dye having a phthalocyanine skeleton. May be used.
In the present invention, either of the above two methods may be adopted, but the former method is preferred.

  (B-1) phthalocyanine dye (β) having a specific ion as a counter ion (A-1) having a phthalocyanine skeleton is synthesized after a phthalocyanine dye having a desired structure is obtained (after obtaining), and exchange of counter ions The desired ion (B) may be introduced by performing the above.

(B) In the case of a method in which a salt (α) of a specific ion and a counter ion other than a phthalocyanine dye is added and (B) the specific ion is included in the first ink composition, a salt is formed. Examples of counter ions other than the phthalocyanine dyes used in the following are listed below.
That is, fluoride ion, chloride ion, bromide ion, iodide ion, p-toluenesulfonic acid ion, methanesulfonic acid ion and the like can be mentioned, among which chloride ion and bromide ion are preferable.

(B) It is preferable that the density | concentration (content) in the 1st ink composition of a specific ion is 0.1 mass%-20 mass% with respect to an ink composition, and 0.1 mass%-10 mass. %, More preferably 0.1% by mass to 5% by mass.
When the content is 0.1% by mass or more, the dyeing property of the first ink composition is increased. On the other hand, when the content is 20% by mass or less, problems such as clogging are less likely to occur when the ink composition is used for inkjet.

[(A-1) Phthalocyanine dye having phthalocyanine skeleton]
The present invention is characterized in that the first ink composition contains (A-1) a phthalocyanine dye having a phthalocyanine skeleton.
Hereinafter, the phthalocyanine dye having a phthalocyanine skeleton is simply referred to as “(A-1) phthalocyanine dye” as appropriate and will be described in detail.
As the phthalocyanine dye, any dye having a phthalocyanine skeleton may be used, but a phthalocyanine acid dye is preferably used.

In the present invention, the (A-1) phthalocyanine dye is particularly preferably a compound represented by the following general formula (P1) or (P2) from the viewpoint of good hue and excellent fastness.
First, the compound represented by general formula (P1) is demonstrated.

In the general formula (P1), X ^{1 to} X ⁴ each independently represents an oxygen atom or a sulfur atom. R ^{1 to} R ⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. P ^{1 to} P ⁴ each independently represents an aromatic ring, and the aromatic ring is a halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, alkyl Oxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfo group Sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl Group, Sill group, an ionic hydrophilic group, a cyano group, a hydroxy group, a nitro group, an amino group, which may have a carbonyl group, and a substituent selected from carbonylamino group. n ¹ ~ ⁴ each independently represents an integer of 0 to ^4, the sum of n 1 ~n ⁴ is at least 1. However, the structure of the general formula (P1) includes at least two ionic hydrophilic groups.

In the general formula (P1), X ^{1 to} X ⁴ are preferably oxygen atoms from the viewpoint of not decreasing the color density (OD) of the cyan region.

In the general formula ^(P1), the alkyl group and aryl group represented by R 1 to R ⁴ have the general formula (I) to be described ^later, an alkyl group and an aryl group as defined represented by R 1 to R ⁴ The preferred embodiment is also the same.
In the general formula (P1), examples of the heteroaryl group represented by R ^{1 to} R ⁴ include imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, and the like.

In the general formula (P1), the aromatic ring represented by P ^{1 to} P ⁴ represents a condensed aromatic ring that may have a hetero atom. Specific examples include a benzene ring, naphthalene ring, pyridine ring, pyrazine ring, imidazole ring, pyrimidine ring, pyrazole ring, quinoline ring, isoquinoline ring, benzothiazole ring, and indole ring. Among these, a benzene ring, a naphthalene ring, a pyridine ring, or a pyrazine ring is preferable, and a benzene ring is more preferable.
Of the four aromatic rings represented by P ^{1 to} P ⁴ , at least three are preferably benzene rings. If three of the four are benzene rings, the dye absorption is near 600 nm, and the color density (OD) in the cyan region is unlikely to decrease.
P ^{1 to} P ⁴ are a halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, alkyloxy group, aryloxy group, acylamino group, alkylamino Group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfo group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy Group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group, ionic hydrophilic group, cyano Which may have a substituent selected from a hydroxy group, a nitro group, an amino group, a carbonylalkyl group, and a carbonylamino group, and has the same meaning as the substituent T that the phthalocyanine skeleton may further have. It is.

  M in the general formula (P1) represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. In the general formula (P1), the metal element, metal oxide, metal hydroxide, or metal halide represented by M is synonymous with that in the general formula (I) described later, and the preferred embodiments are also the same. .

  The structure of the general formula (P1) includes at least two ionic hydrophilic groups, and the ionic hydrophilic group has the same meaning as the ionic hydrophilic group in the general formula (I) described later. The preferred embodiment is also the same.

In the general formula (P1), n ^{1 to} n ⁴ each independently represents an integer of 0 to 4, and the total sum of n ^{1 to} n ⁴ is at least 1. If one or more are not introduced, the light resistance which is the effect of the present invention cannot be maintained. Preferably, n ^{1 to} n ⁴ each independently represents an integer of 0 to 3, and the sum of n ^{1 to} n ⁴ is less than 4, more preferably, n ^{1 to} n ⁴ are each independently 0 to 3 An integer is represented, and the sum of n ^{1 to} n ⁴ is 2 to 3. When the total of n ^{1 to} n ⁴ is 2 to 3, the hue as cyan is good.
The compound represented by the general formula (P1) is to be synthesized as a mixture, the sum of n ¹ ~n ⁴ is the average of such mixtures.

  The compound represented by the general formula (P1) is preferably a compound represented by the following general formula (I).

In general formula (I), R ^{1 to} R ⁴ each independently represents a sulfo group, an alkyl group, an aryl group, or —XR ¹⁰ . Here, X represents an oxygen atom or a sulfur atom. R ¹⁰ represents an alkyl group or an aryl group. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. n ^{1 to} n ⁴ each independently represents an integer of 0 to 4, and the total sum of n ^{1 to} n ⁴ is at least 1. However, the structure of the general formula (I) includes at least two ionic hydrophilic groups, at least one of R ^{1 to} R ⁴ is —XR ¹⁰ , and R ¹⁰ is at least one ionic hydrophilic group. Has a sex group.
Note that R ^{1 to} R ⁴ , R ¹⁰ , and the phthalocyanine skeleton may further have a substituent.

The compound represented by the general formula (I) contains at least two ionic hydrophilic groups. When the number of ionic hydrophilic groups is less than 2, the compound (dye) does not dissolve in water, and an ink composition cannot be obtained.
The number of ionic hydrophilic groups possessed by the compound represented by formula (I) is preferably 2 to 3. Thus, when the number of ionic hydrophilic groups is 2 to 3, the color density (OD) in the cyan region is unlikely to decrease.
Specific examples of the ionic hydrophilic group include a carboxyl group, a sulfo group, and a phosphate group.

When the compound represented by the general formula (I) has a carboxyl group, a sulfo group, or a phosphate group as an ionic hydrophilic group in the molecule, these groups are , May have a counter cation. As the counter cation, for example, metal ions such as Li, Na, and K, (B) a group having a quaternary salt structure of nitrogen containing a specific ion, and a group having a quaternary salt structure of phosphorus are used.
In addition, the compound represented by general formula (I) should just have two or more ionic hydrophilic groups somewhere in the molecular structure. Specifically, the phthalocyanine skeleton may have an ionic hydrophilic group as a substituent, and the ionic hydrophilic group may be directly bonded to the phthalocyanine skeleton, or R ^{1 to} R ⁴ or R described later. ¹⁰ may have an ionic hydrophilic group as a substituent. The ionic hydrophilic groups having two or more in the molecular structure may be the same or different.

As the ionic hydrophilic group, a sulfo group is most preferable.
Hereinafter, the compound represented by the general formula (I) will be described with respect to an embodiment in which the ionic hydrophilic group is a sulfo group. However, the explanation is that the ionic hydrophilic group is a carboxyl group, a phosphate group, or the like. This also applies to a group other than the sulfo group.
The sulfo group and the sulfo group (sulfonate group) forming a salt are also collectively referred to as “SO ₃ Z”. In SO ₃ Z, Z represents a hydrogen atom or a monovalent counter cation. Examples of the monovalent counter cation represented by Z include Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ^+, and the aforementioned (B) specific ion.

In the general formula (I), the sulfo group represented by R ^{1 to} R ⁴ may form a salt as described above. When R ¹ to R ⁴ is represented by -SO ₃ Z, -SO ₃ Z is bonded directly to the phthalocyanine skeleton (Pc), such compounds have the structure represented by Pc-SO ₃ Z .
As described later, in the compound represented by the general formula (I), it is preferable that —SO ₃ Z is not directly bonded to the phthalocyanine skeleton.

In general formula (I), examples of the alkyl group represented by R ^{1 to} R ⁴ include an alkyl group having 1 to 12 carbon atoms, which may be linear or branched. It may be annular.
Specific examples include a methyl group, an ethyl group, a butyl group, an isopropyl group, a t-butyl group, a cyclohexyl group, and a dodecyl group. The alkyl group may further have a substituent.
Among these, a linear or branched alkyl group is preferable, and the number of carbon atoms is preferably 1-8.

In general formula (I), examples of the aryl group represented by R ^{1 to} R ⁴ include aryl groups having 6 to 12 carbon atoms.
Specifically, a phenyl group, a naphthyl group, etc. are mentioned, for example. The aryl group may further have a substituent.
Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

X in —XR ¹⁰ in the general formula (I) represents an oxygen atom (O) or a sulfur atom (S), and is preferably an oxygen atom in that the color density (OD) in the cyan region is not lowered. .

In -XR ¹⁰ in the general formula (I), the alkyl group represented by R ^10, include alkyl groups having 1 to 12 carbon atoms, be linear, a branched Alternatively, it may be annular.
Specific examples include a methyl group, an ethyl group, a butyl group, an isopropyl group, a t-butyl group, a cyclohexyl group, and a dodecyl group. The alkyl group may further have a substituent.
Among these, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable. Moreover, 1-8 are preferable and, as for the number of carbon atoms, 1-4 are more preferable.

In ^{-XR 10} in the general formula ^(I), the aryl group represented by ^{R 10,} an aryl group having 6 to 12 carbon atoms.
Specifically, a phenyl group, a naphthyl group, etc. are mentioned, for example. The aryl group may further have a substituent.
Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

In addition, the compound represented by general formula (I) has a structure in which at least one of R ^{1 to} R ⁴ in general formula (I) is —XR ¹⁰ and R ¹⁰ has at least one sulfo group. . The sulfo group may form a salt.
Hereinafter, the “group represented by —XR ¹⁰ and R ¹⁰ having at least one sulfo group” is also referred to as “specific sulfo group”.
The specific sulfo group can be represented by the following structural formula (s-1).

-XR ¹¹ (SO ₃ Z) m (s-1)
[In Structural Formula (s-1), X represents an oxygen atom or a sulfur atom, Z represents a hydrogen atom or a monovalent counter cation, and m represents the number of SO ₃ Z.
R ¹¹ is an m + 1 valent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an m + 1 valent aromatic hydrocarbon group having 6 to 12 carbon atoms. ]

R ¹¹ in the structural formula (s-1) corresponds to an m + 1 valent group obtained by removing m hydrogen atoms from R ¹⁰ in the general formula (I), and a preferred embodiment of the number of carbon atoms of R ¹¹ is In accordance with R ¹⁰ in formula (I). That is, when R ¹¹ is an aliphatic hydrocarbon group, the preferred number of carbon atoms is 1-8, and the more preferred number of carbon atoms is 1-4.
M in the structural formula (s-1) is the number of SO ₃ Z that can be bonded to R ¹¹ , and an integer of 1 or more can be selected.

R ¹ to R ⁴ in the general formula (I), to only one may be a particular sulfo group, it may be all the specified sulfo group. In the case where a plurality of R ¹ to R ⁴ each formula the compound of formula (I) are molecules, such as a plurality of R ^1, to only one may be a particular sulfo group, all May be a specific sulfo group.

The number of SO ₃ Z (including a specific sulfo group) contained in the compound represented by the general formula (I) is 2 or more in total from the viewpoint of solubility of the compound (dye) in water. The number of the group [XR ¹¹ (SO ₃ Z) m] may be one or more among them. When the compound represented by the general formula (I) has a specific sulfo group, light resistance can be obtained when printing is performed on nylon, which is a polyamide fiber.
The number of specific sulfo groups is preferably less than 4. When the number of the specific sulfo groups is less than 4, the absorption wavelength of the dye is difficult to shift to the long wavelength side, and it is difficult to exhibit a green color. Therefore, the color density (OD) in the cyan region is difficult to decrease. The number of specific sulfo groups is more preferably 2-3.

In the general formula ^(I), n 1 ~n ⁴ each independently represents an integer of 0 to ^4, the sum of n 1 ~n ⁴ it is at least 1. Preferably, n ^{1 to} n ⁴ each independently represents an integer of 0 to 4, and the sum of n ^{1 to} n ⁴ is 1 to 4, more preferably, n ^{1 to} n ⁴ are each independently 0 to 4 represents an ^integer, the sum of n 1 ~n ⁴ is 2-4. More ^preferably, n 1 ~n ⁴ represents an integer of 0 to 3 each independently ^is, the sum of n 1 ~n ⁴ is 2-3.

In addition, the following substituent T can be mentioned as a substituent which R < ¹ > -R < ⁴ >, R < ¹⁰ > and a phthalocyanine skeleton may have further.

As the substituent T,
A halogen atom (for example, chlorine atom, bromine atom);
C1-C12 linear or branched alkyl group (for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl), carbon number 7 to 18 aralkyl groups (for example, benzyl, phenethyl), alkenyl groups having 2 to 12 carbon atoms (for example, phenylvinyl), linear or branched alkynyl groups having 2 to 12 carbon atoms (for example, acetylinyl) ), A cycloalkyl group having 3 to 12 carbon atoms which may have a side chain (for example, cyclopentyl, cyclohexyl), a cycloalkenyl group having 3 to 12 carbon atoms which may have a side chain (for example, cyclo Hexenyl);
Monocyclic or polycyclic aryl groups having 6 to 12 carbon atoms (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, naphthyl);
A monocyclic or polycyclic heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl as a 5-membered monocyclic ring, 2-pyridyl, 3- Pyridyl, 2-pyrimidinyl and, as the polycycle, 2-benzothiazolyl);

An alkyloxy group having 6 to 12 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy);
An aryloxy group having 6 to 12 carbon atoms (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl);

An acylamino group (eg, acetamide, benzamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide);
An alkylamino group having 6 to 12 carbon atoms (for example, methylamino, butylamino, diethylamino, methylbutylamino);
Anilino groups (eg phenylamino, 2-chloroanilino;
A ureido group (eg phenylureido, methylureido, N, N-dibutylureido);
A sulfamoylamino group (eg, N, N-dipropylsulfamoylamino);

An alkylthio group having 6 to 12 carbon atoms (for example, methylthio, octylthio, 2-phenoxyethylthio);
An arylthio group having 6 to 12 carbon atoms (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio);

An alkyloxycarbonylamino group having 6 to 12 carbon atoms (for example, methoxycarbonylamino);
Sulfonamide groups (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane);
A carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl);

A sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl);
A sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl);

An alkyloxycarbonyl group having 6 to 12 carbon atoms (for example, methoxycarbonyl, butyloxycarbonyl);
A heterocyclic oxy group (eg, 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);
A silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy);
An aryloxycarbonylamino group having 6 to 12 carbon atoms (for example, phenoxycarbonylamino);

Imido 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);
A sulfinyl group (eg, 3-phenoxypropylsulfinyl); a phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl);
An aryloxycarbonyl group having 6 to 12 carbon atoms (for example, phenoxycarbonyl);
An acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl);
Ionic hydrophilic group (for example, carboxyl group, sulfo group, quaternary ammonium group);
Other examples include a cyano group, a hydroxy group, a nitro group, an amino group, a carbonylalkyl group, and a carbonylamino group.

In general formula (I), M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
Examples of the metal element represented by M include 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, etc. are mentioned.

Preferred examples of the metal oxide represented by M include VO and GeO.
Moreover, as a metal hydroxide represented by M, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc. are mentioned preferably.
Furthermore, examples of the metal halide represented by M include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, and ZrCl.

  Among the above, M in the general formula (I) is preferably a metal element, more preferably Cu, Ni, Zn, or Al, and most preferably Cu.

Preferred combinations of R ^{1 to} R ⁴ , R ¹⁰ , n ^{1 to} n ⁴ , and M in the general formula (I) are R ^{1 to} R ⁴ , R ¹⁰ , n ^{1 to} n ⁴ , and preferred embodiments of M, respectively. It is a combination.

The ^R 1 to R ⁴ in general formula (I), among the above, the alkyl group is preferably an aryl group, or ^{-XR 10} above. That is, it is preferable that the sulfo group or the sulfo group forming a salt (that is, —SO ₃ Z) is not directly bonded to the phthalocyanine skeleton. Since —SO ₃ Z is not directly bonded to the phthalocyanine skeleton, light resistance is further improved during nylon printing, which is a polyamide fiber.

  For example, each of the following compounds (A-1) and (A-2) is a sulfo group that forms a salt with “two phenoxys” on a phthalocyanine skeleton (M is Cu in the skeleton represented by the structural formula Pc). It has 4 “sulfonic acid Na”.

Compound (A-1) is a compound represented by general formula (I) in which SO ₃ Na is bonded to the benzene ring of the phenoxy group bonded to the phthalocyanine skeleton.
Since compound (A-2) has two SO ₃ Na bonded to the benzene ring of the phenoxy group, it is a compound represented by general formula (I) as in compound (A-1). A-2) also has two SO ₃ Nas directly bonded to the phthalocyanine skeleton.

  In contrast between the compound (A-1) and the compound (A-2), the compound (A-1) is contained rather than printing using the first ink composition containing the compound (A-2). In the case of printing using the first ink composition, the light resistance of the dyed portion on the nylon when printing on nylon, which is a polyamide fiber, was better. Therefore, in the comparison between the compound (A-1) and the compound (A-2), the structure of the compound (A-1) is preferable.

Therefore, R ^{1 to} R ⁴ in the general formula (I) are more preferably —XR ¹⁰ . At this time, ^{-XR 10 may, -XR 10 in which R 10} has at least one sulfo group, i.e., structure (s-1) _{^{[- X-R 11 (SO 3}} Z) m ] particular sulfo represented by It is preferably a group.
Specifically, the compound represented by the general formula (I) is preferably a dye represented by the general formula (II).

In general formula (II), X represents an oxygen atom or a sulfur atom, Z represents a hydrogen atom or a monovalent counter cation, and m represents the number of SO ₃ Z.
R ¹¹ is an m + 1 valent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an m + 1 valent aromatic hydrocarbon group having 6 to 12 carbon atoms.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. n ⁵ represents an integer of 1 to 16, and the product of m and n ⁵ (m × n ⁵ ) is 2 or more.

In the general formula (II), X, Z, m, R 11 has the same meaning X, Z, ^m, and ^{R 11} in the structural formula of the above (s-1), a preferable embodiment thereof is also the same.
M in the general formula (II) has the same meaning as M in the general formula (I), and preferred embodiments thereof are also the same.
In the general formula (II), n ⁵ is the number of specific sulfo groups that can be substituted on the four benzene rings of the phthalocyanine skeleton, and is 16 at the maximum. However, since the compound represented by the general formula (I) (the dye represented by the general formula (II) has at least two sulfo groups in the molecular structure, the product of m and n ⁵ (m × n ⁵ ) is 2 or more.

  Moreover, it is also preferable that the compound represented by the said general formula (P1) is a compound represented by the following general formula (Y).

In the general formula (Y), X ³¹ represents a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkyloxy group, an aryloxy group, or an acylamino group. Group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfo group, sulfonyl group, alkyloxycarbonyl group , Heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group, ionic hydrophilic sex Represents a group, cyano group, hydroxy group, nitro group, amino group, carbonylalkyl group, or carbonylamino group, preferably a halogen atom, aryloxy group, alkylthio group, arylthio group, sulfonamido group, sulfo group, or sulfonyl group And more preferably an aryloxy group, a sulfonamide group, a sulfo group, or a sulfonyl group.
In the general formula (Y), when a plurality of X ³¹ are present, they may be the same as or different from each other. Incidentally, in the general formula (Y), the above groups represented by X ³¹ are as defined further substituent which may be possessed by the phthalocyanine skeleton of the above.

  The compound represented by the general formula (Y) includes at least two ionic hydrophilic groups. The ionic hydrophilic group in general formula (Y) is synonymous with the ionic hydrophilic group in the above general formula (I), and its preferable aspect is also the same.

  In general formula (Y), A represents an oxygen atom or a sulfur atom, and when there are a plurality thereof, they may be the same or different. In view of not decreasing the color density (OD) of the cyan region, an oxygen atom is preferable.

In formula (Y), ^{M 1} is, Cu is a metal element, represents Zn, Ni, or Co, more preferably Cu.
In formula (Y), M ² represents a hydrogen atom or a monovalent counter cation. Examples of the monovalent counter cation represented by M ² include Li ⁺ , K ⁺ , Na ⁺ , NH ₄ ^+, and (B) specific ions described above. Among these, (B) Li ⁺ , K ⁺ , and Na ⁺ are preferable when the ions are not specific ions.
In the general formula (Y), when a plurality of M ² are present, they may be the same as or different from each other.

In the general formula (Y), R ³¹ has the same meaning as X ³¹ and preferably represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.
In the general formula (Y), examples of the halogen atom represented by R ³¹ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
In the general formula (Y), examples of the alkyl group represented by R ³¹ include a linear or branched alkyl group having 1 to 12 carbon atoms, specifically a methyl group, an ethyl group, and a propyl group. Group, isopropyl group, t-butyl group, 2-methanesulfonylethyl group, 3-phenoxypropyl group, trifluoromethyl group and the like.
In the general formula (Y), examples of the alkoxy group represented by R ³¹ include an alkoxy group having 1 to 10 carbon atoms, specifically, a methoxy group, an ethoxy group, an isopropyloxy group, a butoxy group, and 2-ethylhexyl. An oxy group, a hexyl group, etc. are mentioned.

In the general formula (Y), the aryloxy group represented by R ³¹ is, for example, an aryloxy group having 6 to 12 carbon atoms, specifically, (for example, phenoxy, 2-methylphenoxy, 4-t- Examples include butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl and the like.
In the general formula (Y), examples of the alkylthio group represented by R ³¹ include an alkylthio group having 6 to 12 carbon atoms, specifically, methylthio, octylthio, and 2-phenoxyethylthio.
In the general formula (Y), examples of the arylthio group represented by R ³¹ include an arylthio group having 6 to 12 carbon atoms, specifically, phenylthio, 2-butoxy-5-t-octylphenylthio, 2- Carboxyphenylthio etc. are mentioned.
In the general formula (Y), when there are a plurality of R ^{31 s} , they may be the same as or different from each other. R ³¹ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms. In general formula (Y), R ³¹ is preferably in the para position of SO ₃ M ² from the viewpoint of ease of synthesis of the compound.

In the general formula (Y), l ³¹ represents an integer of 0 or more, and is preferably 1. M ³¹ represents an integer of 0 or more, and is preferably 0. Further, n ³¹ represents an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4, and most preferably 4. The larger the number n ³¹ represents, dyeing property is improved.

  The compound represented by the general formula (Y) is preferably a compound represented by the following general formula (Z).

X ⁴¹ in the general formula (Z) has the same meaning as X ³¹ in the above general formula (Y), and the preferred embodiments are also the same.
M ² in the general formula (Z) has the same meaning as M ² in the above general formula (Y), preferable embodiments thereof are also the same.
R ⁴¹ in the general formula (Z) represents an alkyl group. The alkyl group has the same meaning as the alkyl group represented by R ³¹ in the above general formula (Y), preferable embodiments thereof are also the same.
M ⁴¹ and n ⁴¹ in the general formula (Z) have the same meanings as m ³¹ and n ³¹ in the above general formula (Y), respectively, and preferred embodiments thereof are also the same.

When the compound represented by the general formula (Y) is used in the first ink composition, a dyed portion having excellent light resistance can be obtained when used for printing nylon, which is a polyamide fiber. Moreover, the dyeing | staining part containing the compound represented by general formula (Y) is excellent also in dyeing property. That is, according to the first ink composition containing the compound represented by the general formula (Y), it is possible to achieve both light resistance and dyeing property in printing of nylon, which is a polyamide fiber. Although this mechanism of action is not clear, it is presumed as follows.
The oxygen atom constituting —SO ₃ M ² on the aryl group introduced into the phthalocyanine ring and the hydrogen atom on the phthalocyanine ring interact in a hydrogen bond, so that the aryl group is perpendicular to the phthalocyanine ring plane. Stand in. The association between the phthalocyanine rings is inhibited by the vertically standing aryl group, so that the phthalocyanine dye is easily present as a monomer in the ink solution. When the phthalocyanine dye is converted into a monomer, it is presumed that the penetration rate into the fiber is increased and the dyeing property is improved.
The inventors have confirmed by computational chemistry that the aryl group stands perpendicular to the phthalocyanine ring plane. Further, it has been confirmed by measuring the visible absorption spectrum of the ink solution that the aryl group stands perpendicular to the plane of the phthalocyanine ring so that the phthalocyanine dye is easily monomerized in the ink solution.

  Specific examples (1) to specific examples (35) of the dye, which is a compound represented by the general formula (I), and compounds 001 to 011 are shown below, but the present invention is limited to the following specific examples and compounds. Is not to be done.

Specific example (1) to specific example (9), specific example (15), and specific example (18) to specific example (34) are examples of —O—Ph—SO ₃ Na shown in each specific example. The specific sulfo group [in the specific example (19) and the specific example (20), further —SO ₃ Na] is bonded to the carbon atom bonded to the hydrogen atom of the four benzene rings in the phthalocyanine skeleton. Shows that it is replaced by a hydrogen atom.
The specific sulfo group or —SO ₃ Na may be concentrated and bonded to any one of the four benzene rings, or may be bonded to separate benzene rings. However, for example, when “—H” is shown in the benzene ring of the phthalocyanine skeleton as in the specific example (15), the carbon atom to which the hydrogen atom represented by the “—H” is bonded. No specific sulfo group is bound to.

  In specific examples (10) to (14), specific example (16), and specific example (17), the specific sulfo group may be directly bonded to the benzene ring of the phthalocyanine skeleton, or the phthalocyanine skeleton. The phenoxy group bonded to the benzene ring or the hydrogen atom of the carbon atom of the methoxy group may be replaced with the carbon atom of the phenoxy group or methoxy group.

Then, the synthesis example of the compound represented by general formula (P1) is demonstrated.
A synthesis method of the specific example (10), the specific example (28a) which is one of the specific examples (28), and the specific example (29a) which is one of the specific examples (29) will be described as an example. .
In specific example (10), sulfonic acid was introduced by sulfonation after phthalocyanine cyclization using phenoxyphthalonitrile, whereas in specific example (28a) and specific example (29a), sulfonic acid was substituted. It is synthesized by cyclizing phenoxyphthalonitrile. The specific dye can be synthesized by any method. However, when it is desired to limit the position of the sulfonic acid, the latter synthesis method is more appropriate.

[Synthesis Example of Specific Example (10)]
After adding 0.6 mL of acetic acid and 19 g of triethyl orthoacetate to 70 mL of diethylene glycol, 3-phenoxyphthalonitrile (13 g) and phthalonitrile (2.6 g) are continuously mixed and heated to an internal temperature of 100 ° C. did. CuCl ₂ (2.7 g) and ammonium benzoate (22 g) were added to the resulting reaction mixture, and the mixture was stirred at an internal temperature of 100 ° C. for 6 hours.

Next, the obtained mixture was cooled to an internal temperature of 90 ° C., and 7 mL of concentrated hydrochloric acid was added dropwise to the mixture. Thereafter, 100 mL of methanol was further dropped and crystallized. The obtained crystals were dried to obtain 6 g of crude crystals (10A).
3.5 g of crude crystals and 22.5 mL of sulfuric acid were mixed, and 2.5 mL of fuming sulfuric acid was added dropwise to the mixture while being heated and stirred at 60 ° C., followed by stirring at 60 ° C. for 3 hours. 100 mL of water was added to the resulting reaction solution and cooled to room temperature. The precipitated crude crystals were filtered or washed with water, and 1N-NaOH aqueous solution was added until pH 9.5 was dissolved. After stirring at 50 ° C. for 60 minutes, dust was collected and filtered, and 500 mL of isopropyl alcohol was added dropwise to the filtrate for crystallization to obtain 7 g of Compound [Specific Example (10)].
The absorption wavelength (λmax) when 1 mg of the obtained compound [specific example (10)] was dissolved in ultrapure water was 681 nm.

[Synthesis Example of Specific Example (28a)]
To 100 mL of diethylene glycol, 0.5 mL of acetic acid and 20 g of triethyl orthoacetate were added at room temperature, and then the following compound A (16 g) and phthalonitrile (6.4 g) were continuously mixed and heated to an internal temperature of 100 ° C. CuCl ₂ (2.5 g) and ammonium benzoate (22 g) were added to the resulting reaction mixture, and the mixture was stirred at an internal temperature of 100 ° C. for 15 hours.

  Next, the obtained mixture was cooled to an internal temperature of 90 ° C., and 7 mL of concentrated hydrochloric acid was added dropwise to the mixture. Thereafter, 350 mL of isopropyl alcohol was further dropped and crystallized. The obtained crystals were dried to obtain 10 g of crude crystals.

After dissolving 10 g of crude crystals in 100 mL of ion-exchanged water, 2N-NaOH aqueous solution was added until pH 9.5. After stirring at 50 ° C. for 60 minutes, dust was removed and filtered. Thereafter, 500 mL of isopropyl alcohol was added dropwise to the filtrate and crystallized to obtain 3 g of a compound [specific example (28a)].
The absorption wavelength (λmax) when 1 mg of the obtained compound [specific example (28a)] was dissolved in ultrapure water was 622 nm.

[Synthesis Example of Specific Example (29a)]
In the synthesis example of specific example (28a), compound [specific example] was used in the same manner except that “compound A (32 g)” was used instead of “compound A (16 g) and phthalonitrile (6.4 g)”. (29a)] was obtained.
The absorption wavelength (λmax) when 1 mg of the obtained compound [specific example (29a)] was dissolved in ultrapure water was 686 nm.

Next, the compound represented by the following general formula (P2) will be described.
In this compound, the hindered amine structure portion is substituted on the tetraazaporphyrin skeleton via the linking group L ¹⁰¹ , so that the color of the dyed portion and the light resistance thereof are enhanced, and SO ₃ can be placed at any position. By substituting M, solubility in an ink composition prepared in an aqueous system is maintained.

In General Formula (P2), Y ^{101 to} Y ¹¹² each independently represent —CH— or a nitrogen atom. ^However, the number of nitrogen atoms in each group of ^{Y 101 ~Y 104, Y 105 ~Y} 108, and ^Y 109 ^{to Y 112} is an integer of 0-2. R ¹⁰¹ represents a hydrogen atom, an oxygen radical (—O ·), a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and R ¹⁰² and R ¹⁰³ are each independently a carbon atom. A secondary alkyl group having 1 to 20 carbon atoms or a tertiary alkyl group having 1 to 20 carbon atoms is represented. Further, any one of R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring. L ¹⁰¹ represents an alkylene group, —O—, —S—, —NR ²⁰¹ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ²⁰¹ —, —CONR ²⁰¹ —, —SiR ²⁰¹ ₂ —. , An arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these groups. R ²⁰¹ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. One bond of L ¹⁰¹ is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, and the other bond is tetraaza It is bonded to the tetraazaporphyrin skeleton at the position where either the α-position or β-position hydrogen atom of the 6-membered ring of the porphyrin skeleton is removed. SO ₃ M ¹⁰² is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, or is a 6-membered ring of a tetraazaporphyrin skeleton. It is bonded to the tetraazaporphyrin skeleton at a position where either the α-position or β-position hydrogen atom is removed. doing. M ¹⁰¹ represents a copper atom, a zinc atom, a nickel atom, or a cobalt atom, and M ¹⁰² represents a hydrogen atom or a monovalent counter cation. n ¹⁰¹ and n ¹⁰³ each independently represent an integer of 1 or more.

In the general formula (P2), the number of nitrogen atoms contained in each of the groups Y ^{101 to} Y ¹⁰⁴ , the groups Y ^{105 to} Y ¹⁰⁸ , and the groups Y ^{109 to} Y ¹¹² is an integer of 0 to 2. Although it is, it is preferably 0.
Y ^{101 to} Y ¹¹² may be substituted with X ¹⁰¹ described later.

In General Formula (P2), the alkyl group having 1 to 20 carbon atoms represented by R ¹⁰¹ may be unsubstituted or may have a substituent, and is preferably an alkyl group having 1 to 10 carbon atoms. An alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is particularly preferable. Examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclohexyl group, and an n-hexyl group.
Also, an alkoxy group having 1 to 20 carbon atoms represented by R ¹⁰¹ may be unsubstituted may have a substituent, preferably an alkoxy group having 1 to 10 carbon atoms, 1 to 8 carbon atoms An alkoxy group is more preferable, and an alkoxy group having 1 to 6 carbon atoms is particularly preferable. Examples of the alkoxy group include methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, 2-ethylhexyloxy group, cyclohexyloxy group, n-hexyloxy group and the like.

Among the above, preferable R ¹⁰¹ is a hydrogen atom or an alkyl group.

In General Formula (P2), the secondary alkyl group having 1 to 20 carbon atoms represented by R ¹⁰² and R ¹⁰³ may be unsubstituted or may have a substituent, and 2 having 1 to 10 carbon atoms. A secondary alkyl group is preferable, a secondary alkyl group having 1 to 8 carbon atoms is more preferable, and a secondary alkyl group having 1 to 6 carbon atoms is particularly preferable. Examples of the secondary alkyl group include isopropyl group, s-butyl group, cyclohexyl group and the like.
Moreover, the C1-C20 tertiary alkyl group represented by R ^{< 102>} , R ^<103 > may be unsubstituted or may have a substituent, and a C1-C10 tertiary alkyl group is preferable. A tertiary alkyl group having 1 to 8 carbon atoms is more preferable, and a tertiary alkyl group having 1 to 6 carbon atoms is particularly preferable. Examples of the tertiary alkyl group include a tert-butyl group and a tert-amyl group.

Among the above, preferred R ¹⁰² is a tertiary alkyl group, preferred R ¹⁰³ is a tertiary alkyl group, more preferably R ¹⁰² is a tert-butyl group, and R ¹⁰³ is a tert-butyl group.
Moreover, it is preferable that R ¹⁰² and R ¹⁰³ represent the same group.

In the general formula (P2), “NR ¹⁰¹ R ¹⁰² R ¹⁰³ ” means that when R ¹⁰¹ represents a group other than a hydrogen atom, an oxygen radical, or a hydroxy group, one of the hydrogen atoms in R ^{101 to} R ¹⁰³ is 1 one disengaged linked to ^{L 101 by, when R 101} represents a hydrogen atom, an oxygen radical, or hydroxy ^group, one of hydrogen atoms in ^{R 102} and ^{R 103} is linked with ^{L 101} in one outside it .

Also, any two of R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ may be bonded to each other to form a ring. When forming a ring, it is preferable that each carbon number of R <^101> , R ^<102> , R < ¹⁰³ > couple | bonded with each other is 2-40, More preferably, it is 2-30, More preferably, it is 2-20 Especially preferably, it is 2-10.
Examples of the ring formed include an aziridine ring, piperidine ring, pyrrolidine ring and the like. Of ^{these, R 102} and ^{R 103} represent a tertiary ^{alkyl, embodiments R 102} and ^{R 103} are joined to form a piperidine ring together are preferred.

R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ may be substituted with a substituent represented by X ¹⁰¹ described later.

In general formula (P2), the alkylene group represented by L ¹⁰¹ may be either linear or branched, and may be cyclic. The alkylene group represented by L ¹⁰¹ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, still more preferably an alkylene group having 2 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a dimethylmethylene group, and a divalent cyclohexyl group.
Further, the arylene group represented by L ¹⁰¹ may be unsubstituted or may have a substituent, and is preferably an arylene group having 6 to 12 carbon atoms, particularly preferably an arylene group having 6 carbon atoms. . Examples of the arylene group include the following groups.

In the general formula (P2), the divalent heterocyclic group represented by L ¹⁰¹ may be unsubstituted or may have a substituent, and a heterocyclic group having 3 to 10 carbon atoms is preferable. The heteroatom preferably includes a nitrogen atom, a sulfur atom, an oxygen atom and the like. Examples of the divalent heterocyclic group include the following groups.

L ¹⁰¹ may be substituted with a substituent represented by X ¹⁰¹ described later.
Among them, L ¹⁰¹ preferably represents an alkylene group, —SO ₂ —, —SO ₂ NR ²⁰¹ —, or a divalent group obtained by combining these.

R ²⁰¹ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. When a plurality of R ²⁰¹ are present in L ¹⁰¹ described above, R ²⁰¹ may be different from each other.
The alkyl group represented by R ²⁰¹ may be unsubstituted or substituted, and may be linear, branched, or cyclic. The alkyl group represented by R ²⁰¹ is preferably an alkyl group having 1 to 48 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, Examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1-norbornyl group, and a 1-adamantyl group.

The aryl group represented by R ²⁰¹ may be unsubstituted or substituted, and is preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

The heterocyclic group represented by R ²⁰¹ may be unsubstituted or substituted, and is preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms. Examples of the heterocyclic group include 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole A -1-yl group etc. are mentioned.

In General Formula (P2), one bond of L ¹⁰¹ is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed. The other bond of L ¹⁰¹ is bonded to the tetraazaporphyrin skeleton at a position where either the α-position or β-position hydrogen atom of the 6-membered ring of the tetraazaporphyrin skeleton is removed.

“SO ₃ M ¹⁰² ” in General Formula (P2) is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, or The tetraazaporphyrin skeleton is bonded to the tetraazaporphyrin skeleton at a position where either the α-position or β-position hydrogen atom of the 6-membered ring of the tetraazaporphyrin skeleton is removed.

M ¹⁰¹ in the general formula (P2) is preferably a copper atom or a zinc atom, more preferably a copper atom, from the viewpoint of hue and fastness.

Examples of the monovalent counter cation represented by M ¹⁰² in the general formula (P2) include alkali metal ions such as Li ⁺ , K ⁺ , and Na ⁺ , NH ₄ ⁺ , and (B) specific ions described above. Can be mentioned. Above all, if not the (B) specific ions, in terms of water-soluble, ^Li + alkali metal ^ions, K +, Na ⁺ are preferred, particularly preferably ^Li +, a Na ^+.

n ¹⁰¹ represents an integer of 1 or more, and in terms of dyeability and water solubility, an integer of 1 to 4 is preferable, a positive number of 1 to 3 is more preferable, and an integer of 1 to 2 is particularly preferable.

n ¹⁰³ represents an integer of 1 or more, and from the viewpoint of water solubility, an integer of 1 to 8 is preferable, an integer of 2 to 7 is more preferable, and an integer of 3 to 6 is particularly preferable.

The structural part of the tetraazaporphyrin skeleton, -L ^101- , and-(NR ¹⁰¹ R ¹⁰² R ¹⁰³ ) in the general formula (I) is further substituted with n ¹⁰² substituents X ¹⁰¹ as shown below. It may be a structured.
^{N 102} representing the substitution number of X ¹⁰¹ represents an integer of 0 or more, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, particularly preferably 0-1 integer.

In the following general formula (P2a), the substituent X ¹⁰¹ is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, or tetraaza A structure is shown in which a tetraazaporphyrin skeleton is bonded at a position where either the α-position or β-position hydrogen atom of the six-membered ring of the porphyrin skeleton is removed.

Here, the substituent X ¹⁰¹ will be described.
Examples of the substituent X ¹⁰¹ include a halogen atom (eg, fluorine, chlorine, bromine, preferably chlorine, bromine, more preferably chlorine), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 1 carbon atoms). 24 linear, branched or cyclic alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms) 18 alkenyl groups such as vinyl, allyl, 3-buten-1-yl), aryl (preferably carbon An aryl group having 6 to 48, more preferably 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic ring having 1 to 18 carbon atoms). Groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazole-1- Yl group), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t- (Hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 2 carbon atoms). An alkoxy group such as methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, cycloalkyloxy group (for example, cyclopentyloxy group, cyclohexyloxy group) )), Aryloxy groups (preferably aryloxy groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenoxy group and 1-naphthoxy group), heterocyclic oxy groups (preferably having 1 carbon atom) To 32, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group and 2-tetrahydropyranyloxy group), silyloxy group (preferably having 1 to 32 carbon atoms, More preferably, it is a silyloxy group having 1 to 18 carbon atoms, such as trimethylsilyloxy group, t-butyl A dimethylsilyloxy group, a diphenylmethylsilyloxy group), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, dodecanoyl An oxy group), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cycloalkyloxycarbonyl group). An oxy group (for example, cyclohexyloxycarbonyloxy group)), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonyl An oxy group), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N -Phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, , Methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexyls Honiruokishi group),

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably C1-C24 acyl group, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably C2-C48, more preferably An alkoxycarbonyl group having 2 to 24 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), Aryloxycarbonyl group (preferred Or an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Carbamoyl groups such as carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN -Phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino group, N, N- Dibutylamino group, tetradecylami group, 2-ethylhexylamino group, cyclohexyl Amino group), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group and an N-methylanilino group), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, More preferably, it is a heterocyclic amino group having 1-18, for example, 4-pyridylamino group), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2-24, for example, an acetamide group, Benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, ureido group, N, N-dimethylureido Group, N-phenylureido group), imide group (preferably having 36 or less carbon atoms, more preferably having 24 or less carbon atoms). In the lower imide group, for example, N-succinimide group, N-phthalimide group), alkoxycarbonylamino group (preferably C2-48, more preferably C2-C24 alkoxycarbonylamino group, for example, methoxy Carbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 32 carbon atoms) 24 aryloxycarbonylamino group, for example, phenoxycarbonylamino group), sulfonamido group (preferably 1-48 carbon atoms, more preferably 1-24 carbon sulfonamido group, for example, methanesulfonamido group, Butanesulfo An amide group, a benzenesulfonamide group, a hexadecanesulfonamide group, a cyclohexanesulfonamide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, For example, phenylazo group, 3-pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms). More preferably, it is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 prime atoms, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, ethyl Sulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, 1-naphthylsulfonyl v), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Rufamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, N- (2-ethylhexyl) ) Sulfamoyl group), phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphino It represents an ylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

Of the above, preferred groups are a halogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group, and more preferably a halogen atom, an alkyl group. A sulfonyl group, an arylsulfonyl group and a sulfamoyl group, particularly preferably a sulfamoyl group.
In addition, when the above group is a further substitutable group, it may be substituted with the group described above or a sulfo group (SO ₃ M).

  The compound represented by the general formula (P2) is preferably a compound represented by the following general formula (P2b).

In General Formula (P2b), R ¹⁰¹ represents a hydrogen atom, an oxygen radical (—O ·), a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Represented by R ^101, an alkyl group having 1 to 20 carbon atoms, and alkoxy group having 1 to 20 carbon atoms is represented by ^{R 101} in the general formula (P2), the alkyl group having 1 to 20 carbon atoms, And a C1-C20 alkoxy group, and a preferable aspect is also the same.

In the general formula (P2b), one of n ¹⁰¹ L ¹⁰¹ bonds is released from n ¹⁰¹ hydrogen atoms on the phthalocyanine skeleton (particularly four benzene rings) represented by (a). To join.
Further, the other bond of n ¹⁰¹ L ¹⁰¹ is each a hydrogen atom in the structure represented by (b) (that is, a hydrogen atom in R ¹⁰¹ , four CH ₃ hydrogen atoms, and a six-membered member) Bonding with the structure represented by (b) is made at a position where one of three unsubstituted CH ₂ hydrogen atoms forming a ring is removed. In addition, it is preferable that L ¹⁰¹ is bonded by removing any hydrogen atom of three unsubstituted CH ₂ forming a 6-membered ring in the structure represented by (b).

L ¹⁰¹ in the general formula (P2b) represents an alkylene group, —O—, —S—, —NR ²⁰¹ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ²⁰¹ —, —CONR ²⁰¹ —. , —SiR ²⁰¹ ₂ —, an arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these. R ²⁰¹ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
^{L 101, R 201} in formula (P2b) of the general formula (P2) ^{L 101, R 201} and have the same meanings in the same preferred embodiment also respectively.

M ¹⁰¹ in the general formula (P2b) represents a copper atom, a zinc atom, a nickel atom, or a cobalt atom, and M ¹⁰² represents a hydrogen atom, an ammonium, or an alkali metal atom (for example, a lithium atom, a sodium atom, or a potassium atom). Represent. n ¹⁰¹ and n ¹⁰³ each independently represent a positive number of 1 or more.
^M 101 in the general formula ^(P2b), M ^{102, n 101,} and ^{n 103} is, ^M 101 in the formula ^(1), M ^{102, n 101,} and ^{n 103} and have the same meanings, preferred embodiments also each It is the same.

In the general formula (P2b), n ¹⁰³ “SO ₃ M ¹⁰² ” s are selected from the phthalocyanine skeleton (particularly, four benzene rings) represented by (a) and the structure represented by (b). N ¹⁰³ hydrogen atoms ^{separated from} each other are bonded.

In the general formula (P2b), the phthalocyanine skeleton represented by (a), -L ^101- , and the structure represented by (b) are represented by the general formula (P2a) as in the general formula (I). As indicated, it may be further substituted with n ¹⁰² substituents X ¹⁰¹ .
N ¹⁰² representing the number of substitutions of X ¹⁰¹ represents an integer of 0 or more, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, particularly preferably 0 or 1.

In General Formula (P2b), a preferable structure is that R ¹⁰¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L ¹⁰¹ is a sulfamoyl group, an alkylene group, a sulfonyl group, or a combination of at least two of these. A group, M ¹⁰¹ is a copper atom, M ¹⁰² is an alkali metal atom (particularly a lithium atom, a sodium atom, or a potassium atom), n ¹⁰¹ is 1 to 2, and n ¹⁰³ is 3 to 4. A compound.

  Specific examples of the compound represented by the general formula (P2) are shown below. However, the present invention is not limited to these specific examples.

Then, the synthesis | combining method of the compound represented by general formula (P2) is demonstrated.
As a method for synthesizing the compound represented by the general formula (P2), a method of synthesizing from a phthalic acid derivative and a method of synthesizing from a phthalocyanine can be roughly classified.

-Synthesis from phthalic acid derivatives-
As an example of a method for synthesizing the compound represented by the general formula (P2), there is a method of synthesizing from a phthalic acid derivative. For example, “phthalocyanine-chemistry and function” (Shirai-Kobayashi, p. 1 to p. 62). , Published by IPC Co., Ltd.), "Phthalocyanines-Properties and Applications" (co-authored by CCLeznoff-ABP Lever, p.1-54, issued by VCH) and the like. Specific examples include (1) reaction of phthalonitrile with a metal salt (phthalonitrile method), and (2) reaction of phthalic anhydride or phthalic acid or phthalimide with urea (Weiler method). From the viewpoint of easiness, (1) the phthalonitrile method is preferable.
Examples of a method for obtaining a phthalocyanine compound substituted with various substituents by the phthalonitrile method include a method of cyclizing a mixture of phthalonitrile substituted with various substituents at a desired ratio as described below. Here, the azaphthalocyanine derivative can be obtained by mixing the corresponding raw material azaphthalonitrile and phthalonitrile and cyclizing the phthalocyanine.

  Specific conditions for the cyclization reaction include, as described in JP-A-2009-19209, in a solvent (nitro-based solvents such as nitrobenzene, tolylnitrile-based solvents such as benzonitrile, polyethylene glycol, diethylene glycol and the like Glycol-based solvents, etc.), phthalonitrile, metal salts (chlorides, bromides, iodides, acetates, trifluoromethanesulfonates, etc.), and optionally bases (for example, DBU, etc.) to heat the desired compound Is obtained.

-Synthesis from phthalocyanine-
This method is limited to the introduction of a sulfamoyl group or a sulfo group. For example, as shown in the following scheme, a phthalocyanine can be introduced into a side chain by chlorosulfonylation or sulfonation, amidation or hydrolysis. . Specific methods include, for example, International Application No. 00/17275, International Application No. 00/08103, International Application No. 00/08101, International Application No. 98/41853, and Japanese Patent Application Laid-Open No. 10-36471. Reference can be made to Japanese Patent Publication No. JP-A-2002-522561, US Pat. No. 6,332,918, and the like.

  Confirmation that the compound compound (tetraazaporphyrin-based compound) represented by the general formula (P2) has been synthesized can be performed by mass spectrum (MS) measurement. Moreover, when a dye compound does not have magnetism, NMR measurement can also be used.

The compound represented by the general formula (P2) is a compound exhibiting blue to cyan.
In the compound represented by the general formula (P2), n ¹⁰¹ "-L ^101- (NR ¹⁰¹ R ¹⁰² R ¹⁰³ )" are either α-position or β-position of the 6-membered ring of the tetraazaporphyrin skeleton. However, from the viewpoint of dyeability on the fabric, substitution at the α-position is preferable.

In the present invention, the above-described (A-1) phthalocyanine dye is used in the first ink composition, but such phthalocyanine dye may be used alone or in combination of two or more. May be.
In addition to the (A-1) phthalocyanine dye, the first ink composition may have other coloring that matches the desired hue of the first ink composition as long as the effects of the present invention are not impaired. An agent (dye, pigment, etc.) may further be included.

When other colorants are included, the content of (A-1) phthalocyanine dye is preferably 50% by mass or more, more preferably 80% by mass or more, and further 100% by mass with respect to the total mass of the colorant. That is, it is preferable to contain only (A-1) a phthalocyanine dye.
As the content of the colorant (including (A-1) phthalocyanine dye and other colorant) in the first ink composition, a good color density can be obtained, and the storage stability of the composition Is considered, 1% by mass to 20% by mass is preferable with respect to the total mass of the first ink composition, 4% by mass to 15% by mass is more preferable, and 5% by mass to 15% by mass is still more preferable.

[(C) Water]
In the present invention, (C) water is contained in the first ink composition.
(C) Water is not particularly limited, and may be ion exchange water or tap water.
(C) When the specific ion (B) is a counter ion of (A) phthalocyanine dye, the content of water will be described later as (A) phthalocyanine dye from the total mass of the first ink composition. (D) It becomes the remainder which deducted content with other components (arbitrary component).
In addition, when the (B) specific ion is added to the first ink composition by a salt with a counter ion other than the phthalocyanine dye, (C) the water content is the first ink composition. The balance obtained by subtracting the content of (A) a phthalocyanine dye, (B) a salt of a specific ion and a counter ion other than the phthalocyanine dye, and (D) other components (arbitrary components) described later, from the total mass of the product Become.

[(D) Other ingredients]
In addition to the components (A) to (C) described above, the first ink composition contains components such as an organic solvent, a surfactant, and various additives as other components as required. You may do it.

(Organic solvent)
The organic solvent that can be contained in the first ink composition is preferably an aqueous organic solvent. Examples of the organic solvent include polyhydric alcohols (for example, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene glycol, triethylene glycol, tripropylene glycol, 1 , 2,4-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 1,2-hexanediol, 1,5-pentanediol, 1,2-pentanediol, 2, 2-dimethyl-1,3-propanediol, 1,2-butanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,3-butanediol 2-methyl-1,3-propanediol, etc.), (Eg, ethanolamine, 2- (dimethylamino) ethanol, etc.), monohydric alcohols (eg, methanol, ethanol, butanol, etc.), polyhydric alcohol alkyl ethers (eg, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether) , Triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.), 2,2′-thiodiethanol, amide (For example, N, N-dimethylformamide, etc.), sulfolane, dimethyl sulfoxide, 3-s Sulfur-containing compounds such Horen, heterocycles (e.g., 2-pyrrolidone, N- methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N- ethylmorpholine, etc.), acetonitrile, and the like.
Moreover, said organic solvent may be used independently and may be used together 2 or more types.
The content of the organic solvent in the first ink composition is preferably 1% by mass to 60% by mass and more preferably 2% by mass to 50% by mass with respect to the total mass of the ink composition. preferable.

(Surfactant)
Various surfactants can be used for the first ink composition from the viewpoint of enhancing storage stability, ejection stability, ejection accuracy, and the like. As the surfactant, any of cationic, anionic, amphoteric and nonionic surfactants can be used.

  Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

  Examples of the anionic surfactant include fatty acid soaps, N-acyl glutamates, alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfoacetates, sulfated oils, higher alcohol sulfates, and alkyl phosphates. Etc.

Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like. A suitable example is an amine oxide type such as N, N-dimethyl-N-alkylamine oxide.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sorbitan Examples include fatty acid esters, propylene glycol fatty acid esters, and acetylene glycol. A suitable example is SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant.
In addition, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.

When using each of these surfactants, the surfactant may be used alone or in combination of two or more.
The content of the surfactant in the first ink composition is preferably in the range of 0.001% by mass to 5.0% by mass with respect to the total mass of the ink composition. It is preferable to arbitrarily adjust the surface tension of the object.

(Various additives)
The first ink composition may contain other conventionally known additives. For example, pH adjusters such as acid bases and buffers, fluorescent brighteners, antifoaming agents, lubricants, thickeners, UV absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, specific resistance It is a regulator, a rust inhibitor, an inorganic pigment, a reduction inhibitor, a preservative, an antifungal agent, and the like.

-UV absorber-
Examples of ultraviolet absorbers 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-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-A-56-21141 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 The triazine compounds described in JP-A-8-501291, 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. By containing the ultraviolet absorber, the storability of the image can be improved.

-Anti-fading agent-
As an anti-fading agent, various organic and metal complex anti-fading agents can be used. Examples of organic fading inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Nickel complexes and zinc complexes. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. Compounds described in the patent cited in US Pat. No. 15162, compounds represented by general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137, and US Pat. No. 5,356,443 Can be used. By containing the anti-fading agent, the storability of the image can be improved.

-Antiseptic, antifungal agent-
The first ink composition may contain at least one of a preservative and an antifungal agent in order to maintain long-term storage stability. By containing a preservative or antifungal agent, long-term storage stability can be enhanced. Examples of the preservative and antifungal agent include aromatic halogen compounds (for example, Preventol CMK; manufactured by LANXESS), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL). , PROXEL XL2; manufactured by Arch Chemicals Co., Ltd.).

  In the present invention, in the first ink composition, the fabric dyed with such a composition preferably has a cyan hue, and the hue angle is preferably 200 ° to 260 °. In addition, when the hue of cyan to blue is included, it is preferably 200 ° to 300 °, more preferably 210 ° to 300 °. When the hue in this range is shown, the color density (OD) in the cyan region is unlikely to decrease.

[Second ink composition]
Next, the second ink composition constituting the ink set of the present invention will be described.
The second ink composition contains (A-2) a dye having a skeleton other than the phthalocyanine skeleton, and (C) water, and may further contain other components as necessary.

[(A-2) Dye having skeleton other than phthalocyanine skeleton]
The dye having a skeleton other than the (A-2) phthalocyanine skeleton (hereinafter referred to as (A-2) non-phthalocyanine dye) in the second ink composition may be any, but the polyamide fiber Specifically, from the viewpoint of dyeability and fastness to fabrics containing, specific examples include aryl or heteryl azo dyes, azomethine dyes, methine dyes, quinone dyes, quinophthalone dyes, nitro / nitroso dyes, acridine dyes, acridinone dyes, carbonium It is preferably at least one acid dye selected from the group consisting of dyes, polymethine dyes, and indigo / thioindigo dyes.

In particular, in the present invention, the dye having a skeleton other than the phthalocyanine skeleton in the second ink composition is at least one acid selected from the group consisting of compounds represented by formulas (D1) to (D6). A dye is preferred.
First, the compound represented by the following general formula (D1) or (D2) will be described.

In the general formulas (D1) and (D2), A, B, and C each independently represent an aromatic group or a heterocyclic group. However, at least one — (SO ₃ M) is introduced into the aromatic group or heterocyclic group represented by A, B, and C. Here, M represents a hydrogen atom, an alkali metal ion such as Li ⁺ , K ⁺ , or Na ⁺ , or NH ₄ ⁺ . N is an integer of 1 or more.

In the general formulas (D1) and (D2), A, B, and C each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (note that A and C Is a monovalent group and B is a divalent group).
In general formula (D2), n is an integer of 1 or more. Especially, the compound whose n is 1 or 2 is preferable, and it is preferable that at least 2 or more is a heterocyclic group which may be substituted among A, B, and C at that time. Of these, n = 1 is particularly preferable, and at least B and C are unsaturated heterocyclic groups.

In the case of a monovalent group, the aromatic group represented by A, B, and C means an aryl group and a substituted aryl group, and the aryl group preferably has 6 to 20 carbon atoms, It is more preferable that it is several 6-16. Specifically, the monovalent aromatic group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.
Examples of the monovalent aromatic group include a phenyl group, a naphthyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and an m- (3-sulfopropylamino) phenyl group.
The divalent aromatic group is a divalent aromatic group obtained by removing one hydrogen atom from the monovalent aromatic group. Examples thereof include a phenylene group, a p-tolylene group, and a p-methoxyphenylene group. Group, o-chlorophenylene group, m- (3-sulfopropylamino) phenylene group, naphthylene group and the like.

In addition, as the heterocyclic group represented by A, B, and C, in the case of a monovalent group, a pyridine ring, a pyrazole ring, an imidazole ring, an isothiazole ring, a benzoisothiazole ring, a thiadiazole ring, a thiazole ring, A monovalent group is exemplified by removing one hydrogen atom from a thiazole ring or triazole ring, and a pyridine ring, an isothiazole ring, a benzoisothiazole ring, a thiadiazole ring, or a benzothiazole ring is preferable, and a pyridine ring, Thiazole ring.
Examples of the monovalent heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, 2-furyl group and the like.
The divalent heterocyclic group may be any divalent heterocyclic group obtained by removing one hydrogen atom from the monovalent heterocyclic group.

Any of the above-described aromatic groups and heterocyclic groups may have a substituent, and examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups in addition to — (SO ₃ M). An acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, an ionic hydrophilic group, and the like.

The compound represented by the general formula (D1) or (D2) preferably has 1 to 5 — (SO ₃ M) in one molecule, and 2 to 4 from the viewpoint of water solubility. More preferably it is present.

  The compound represented by the general formula (D1) may be a compound represented by the following general formula (D1-L). That is, the compound represented by the general formula (D1-L) may be a dimer connected by the connecting chain L at the portion B in the general formula (D1).

In General Formula (D1-L), L represents a divalent linking group, and examples of the divalent linking group represented by L include an alkylene group, an arylene group, a heterocyclic residue, —CO—, and —SO _p — ( p is 0, 1, or 2), —NR ⁰ — (R ⁰ represents a hydrogen atom, an alkyl group, or an aryl group), —O—, and a divalent group obtained by combining these groups. Selected from the group.
L may have the substituent or the ionic hydrophilic group mentioned as the substituent substituted with A and B. m is 2.

  Specific examples of the compound represented by the general formula (D1) or (D2) include those shown below, but the present invention is not limited thereto.

  In addition, examples of the compound represented by the general formula (D1) include C.I. I. Acid Yellow 78, C.I. I. Acid red 131 etc. are mentioned.

  Examples of the compound represented by the general formula (D2) include C.I. I. Acid Red 154, C.I. I. Acid red 114 etc. are mentioned.

  Next, the compound represented by the following general formula (D3) will be described.

In General Formula (D3), R ^{301 to} R ³⁰⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. The R ³⁰⁵ to R ³¹⁷ each independently represent a group on the benzene ring, represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, or a phenoxy ^{group, R} 305 to R Any two of ³¹⁷ may be connected to form a ring. However, at least one of R ^{301 to} R ³¹⁷ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m1 represents an integer of 1 to 13.
Each group represented by R ^{301 to} R ³¹⁷ may have a substituent such as a halogen atom, a hydroxyl group, an amino group, an ester group, or a ketone group.

M in the general formula (D3) is preferably an alkali metal ion, and is preferably a Li ion, a Na ion, or a K ion.
M1 is preferably in the range of 1-6.

  Examples of the compound represented by the general formula (D3) include C.I. I. Acid Violet 49, C.I. I. Acid Blue 7 etc. are mentioned.

  Then, the compound represented by the following general formula (D4) is demonstrated.

In General Formula (D4), R ^{401 to} R ⁴⁰⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. R ^{405 to} R ⁴¹⁵ each independently represent a group on a benzene ring, and each represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, or a phenoxy group, and R ^{405 to} R ⁴¹⁵ Any two of them may be linked to form a ring. However, at least one of R ^{405 to} R ⁴¹⁵ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m2 represents an integer of 1 to 11.
Each group represented by R ^{401 to} R ⁴¹⁵ may have a substituent such as a halogen atom, a hydroxyl group, an amino group, an ester group, or a ketone group.

M in the general formula (D4) is preferably an alkali metal ion, and is preferably Li ion, Na ion, or K ion.
M2 is preferably in the range of 1-6.

  Examples of the compound represented by the general formula (D4) include C.I. I. Acid Red 52, C.I. I. Acid Red 289 and the like.

  Then, the compound represented by the following general formula (D5) is demonstrated.

In general formula (D5), R ^{501 to} R ⁵⁰⁶ each independently represents a group on the benzene ring, and are a hydrogen atom, a hydroxy group, an alkyl group that may have a substituent, an aryl group, a heteroaryl group, An alkoxy group, an amino group, or a phenoxy group is represented, and X ¹ and X ² each independently represent —NR ⁵⁰⁷ R ⁵⁰⁸ , —OR ⁵⁰⁹ , or a hydroxy group. Any ^two of R ^{501 to} R ⁵⁰⁶ , X ¹ and X ² may be linked to form a ring. However, at least one of R ^{501 to} R ⁵⁰⁶ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m3 represents an integer of 1 to 6. R ⁵⁰⁷ , R ⁵⁰⁸ , and R ⁵⁰⁹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
Each group represented by R ^{501 to} R ⁵⁰⁹ may have a substituent such as a halogen atom, a hydroxyl group, an amino group, an ester group, or a ketone group.

M in the general formula (D5) is preferably an alkali metal ion, and is preferably a Li ion, a Na ion, or a K ion.
M3 is preferably in the range of 2-4.

  Examples of the compound represented by the general formula (D5) include C.I. I. Acid Violet 43 and the like.

  Subsequently, the compound represented by the following general formula (D6) will be described.

In General Formula (D6), R ⁶⁰¹ and R ⁶⁰² each independently represent an alkyl group, an aryl group, or a heteroaryl group. R ^{603 to} R ⁶⁰⁹ each independently represents a group on the benzene ring, and represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, or a phenoxy group, and R ^{603 to} R ⁶⁰³ Any two of ⁶⁰⁶ and any two of R ^{607 to} R ⁶⁰⁹ may be linked to form a ring. However, at least one of R ^{601 to} R ⁶⁰⁹ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m4 represents an integer of 1 to 7.
Each group represented by R ^{601 to} R ⁶⁰⁸ may have a substituent such as a halogen atom, a hydroxyl group, an amino group, an ester group, or a ketone group.

M in the general formula (D6) is preferably an alkali metal ion, and is preferably a Li ion, a Na ion, or a K ion.
M4 is preferably in the range of 1-6.

  Examples of the compound represented by the general formula (D6) include C.I. I. Acid Red 143 and the like.

In the present invention, the above-described various (A-2) non-phthalocyanine dyes are used in the second ink composition, but these various dyes may be used alone or in combination of two or more. May be used.
Further, in the second ink composition, in addition to the various (A-2) non-phthalocyanine dyes described above, other colorants (dyes and pigments) matched to the desired hue of the second ink composition. Etc.) may be further included.

  The content of the total colorant in the second ink composition is 1% by mass with respect to the total mass of the ink composition when a good color density is obtained and considering the storage stability of the composition. -20% by mass is preferable, 4% by mass to 15% by mass is more preferable, and 5% by mass to 15% by mass is further preferable.

[(C) Water and (D) Other ingredients]
The second ink composition contains (C) water and, if necessary, (D) other components. The (C) water and (D) other components are contained in the first ink composition described above. The preferred examples and preferred amounts are also the same.

[Ink set manufacturing method]
The ink set of the present invention includes (A-1) a first step of preparing a first ink composition containing (A-1) a phthalocyanine dye, (B) a specific ion, and (C) water; A second step of preparing a second ink composition containing a phthalocyanine dye and (C) water. In the first step, (B) a specific ion and (A-1) a phthalocyanine type A first ink composition is prepared using at least one of a salt (α) with a counter ion other than the dye and (A-1) a phthalocyanine dye (β) containing (B) a specific ion as a counter ion. , Can be obtained.

That is, the first ink composition in the present invention includes (B) a specific ion and (A-1) a salt (α) due to a counter ion other than the phthalocyanine dye, and (B) the specific ion as a counter ion. (A-1) It is prepared by using at least one of phthalocyanine dyes (β).
When the salt (α) is used, the first ink composition may be prepared by mixing the salt (α), the (A-1) phthalocyanine dye, and (C) water together. (A-1) A salt (α) may be added to a mixed solution in which a phthalocyanine dye and (C) water are mixed.

In the case of using the salt (α), the substance amount ratio (molar ratio) of the salt containing (B) specific ions to the (A-1) phthalocyanine dye in the first ink composition is 0.5% to 5% is preferable, and 1% to 4% is more preferable.
In the case of using the phthalocyanine dye (β), the substance amount ratio (molar ratio) of (B) specific ions to (A-1) phthalocyanine dye in the first ink composition is 1% to 4%. %, Preferably 2% to 4%.
In addition, you may use together the aspect using a salt ((alpha)), and the aspect using a phthalocyanine dye ((beta)).

[Specific form of ink set]
As a specific form of the ink set of the present invention, as a form of an ink set comprising two color dye inks,
A form comprising: a cyan ink as a first ink composition; and a yellow ink containing the azo dye as a second ink composition;
A form comprising: a cyan ink as a first ink composition; and a magenta ink containing the xanthene dye as a second ink composition;
The form provided with the cyan ink which is a 1st ink composition, and the cyan ink containing the said anthraquinone dye which is a 2nd ink composition, etc. are mentioned.

Furthermore, as a form of an ink set including dye inks of three or more colors,
A form comprising: a cyan ink as a first ink composition; and a yellow ink containing the azo dye as a second ink composition; a magenta ink containing the xanthene dye as a second ink composition; A form with
A magenta ink comprising a cyan ink as a first ink composition and a yellow ink containing the azo dye as a second ink composition, and a magenta ink containing the anthrapyridone dye as a second ink composition It is also possible to adopt a form provided with.
The ink set of the present invention may be an ink set including four or more dye inks using an ink composition containing other dyes as necessary.

[Ink-jet ink]
The ink set of the present invention may be an ink set applied to inkjet.
When the ink set of the present invention is for inkjet, the following additives are added to the first ink composition and the second ink composition as necessary, so that the effects of the present invention are not impaired. It may be contained in a range.

  Examples of the additive applied to the ink jet ink set include a drying inhibitor (wetting agent), a fading inhibitor, an emulsion stabilizer, a penetration accelerator, an ultraviolet absorber, an antiseptic, an antifungal agent, a pH adjuster, Well-known additives, such as a surface tension regulator, an antifoamer, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust inhibitor, a chelating agent, are mentioned. These various additives can be directly added to the ink liquid in the case of water-soluble ink.

(Anti-drying agent)
As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. By containing an anti-drying agent in the ink-jet ink, clogging due to drying of the ink-jet ink can be prevented at the ink ejection port of the nozzle of the ejection head that ejects the ink.
Specific examples of the drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, Polyhydric alcohols typified by acetylene glycol derivatives, glycerin, trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, etc. Lower alkyl ethers of polyhydric alcohols, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl Rusuruhokishido, sulfur-containing compounds such as 3-sulfolene, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
Moreover, a drying inhibitor may be used individually by 1 type, and may be used together 2 or more types.
The content of the drying inhibitor is preferably 10% by mass to 50% by mass with respect to the total mass of the total mass of the ink composition.

(Antidepressant)
Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, and salts thereof.
The antifungal agent may be used alone or in combination of two or more.
The content of the antifungal agent is preferably 0.02% by mass to 1.00% by mass with respect to the total mass of the ink composition.

(PH adjuster)
As the pH adjusting agent, neutralizing agents such as organic bases and inorganic alkalis can be used. By containing a pH adjuster in the ink-jet ink, the storage stability of the ink-jet ink can be improved. The pH adjuster is preferably added so that the pH of the inkjet ink is 6 to 10, and more preferably 7 to 10.

(Surface tension adjusting agent, antifoaming agent)
Examples of the surface tension adjusting agent include various surfactants such as a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Preferred examples of the surfactant are the same as those exemplified in the above-mentioned surfactant column.
As the antifoaming agent, fluorine-based and silicone-based compounds are preferable.

When the ink set of the present invention is used for inkjet, the surface tension of the ink composition is preferably adjusted to 20 mN / m to 70 mN / m, more preferably 25 mN / m to 60 mN / m. The viscosity of the ink composition is preferably adjusted to 40 mPa · s or less, more preferably 30 mPa · s or less, and particularly preferably 20 mPa · s or less.
Surface tension and viscosity 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, a surfactant or the like.

(Chelating agent)
The chelating agent is preferably used for the purpose of preventing the occurrence of precipitates such as precipitates in the ink composition, and for the purpose of improving storage stability and clogging recovery.
When a dye is included in the ink composition, the metal (Ca, Mg, Si, Fe, etc.) contained in the ink composition may cause the generation of precipitates and the reduction of clogging recovery, so that metal ions are reduced. If a copper complex dye is used, the amount of metal ions must be controlled, but if the amount of free copper ions is not controlled, It is known that a reduction in clogging recovery is observed (see Japanese Patent Application Laid-Open Nos. 2000-355665 and 2005-126725, etc.).
The (A-1) phthalocyanine dye in the present invention is preferably a copper complex dye containing copper as a central metal, and free copper ions in the first ink composition are preferably 10 ppm or less, More preferably, it is 0 ppm to 5 ppm.

Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, uramildiacetic acid, and metal salts thereof (for example, sodium salt).
In addition, as a method for controlling the concentration of metal ions and free copper ions, in addition to a method using a chelating agent, a method for increasing the degree of purification of the dye can also be mentioned.

<Printing method>
The textile printing method of the present invention is a textile printing method in which a fabric containing polyamide fibers is dyed by the ink jet method using the above-described ink set of the present invention.
According to the ink set of the present invention, since the balance of dyeing property is excellent compared to the printing by the ink set provided with the ink composition using the conventional general-purpose phthalocyanine dye, the printing having an excellent balance of color is performed. Can do.
First, a fabric to be printed will be described.

[Fabric]
The fabric used in the present invention is a fabric containing polyamide fibers, and specifically, nylon, silk, and wool are more preferable.
In particular, the ink set of the present invention is particularly suitable for nylon printing.

Examples of nylon include various nylons such as nylon 6, nylon 6,6, nylon 6,10, nylon 11 and nylon 12, and any nylon may be used.
The polyamide fiber may be in any form such as a woven fabric, a knitted fabric, or a non-woven fabric.

  The fabric containing the polyamide fiber is preferably 100% polyamide fiber, but may contain a material other than the polyamide fiber. When the fabric includes fibers other than polyamide fibers, the blend ratio of the polyamide fibers is preferably 30% or more, and more preferably 50% or more. As a material other than the polyamide fiber, for example, a blended woven fabric or a blended nonwoven fabric with rayon, cotton, acetate, polyurethane, acrylic fiber or the like can be used as the textile for printing in the present invention.

  There are suitable ranges for the physical properties of polyamide fibers and polyamide fibers constituting the fabric. For example, in the case of nylon, the average thickness of the nylon fibers is preferably 1d to 10d (denier), more preferably Is controlled to 2d to 6d, and the average thickness of the nylon yarn composed of the nylon fibers is preferably controlled to 20d to 100d, more preferably 25d to 80d, and even more preferably 30d to 70d. A fabric is used. In the case of silk, the average thickness of the silk fiber is preferably controlled to 2.5d to 3.5d, more preferably 2.7d to 3.3d as a characteristic of the fiber itself. The average thickness of the silk thread is preferably controlled to 14d to 147d, more preferably 14d to 105d, and a fabric made by a known method is preferably used.

As described above, the textile printing method of the present invention dyes a fabric by applying the ink set of the present invention to a fabric containing polyamide fibers by an inkjet method.
Hereafter, each process of the textile printing method of this invention is demonstrated in detail.

[Ink application process]
The ink set of the present invention is applied to the fabric by an ink jet method (hereinafter, referred to as “ink applying step” as appropriate). The ink jet method is a method of printing an image by ejecting ink from an ink jet recording head to apply ink to a fabric. Below, the textile printing method which provides an ink with the inkjet method is demonstrated.
Further, in the textile printing method of the present invention, pre-treatment may be performed so that the fixation of the colorant to the fabric is further increased when the ink set is applied to the fabric in the ink application step.

[Pretreatment process]
The textile printing method of the present invention may be configured to have a pretreatment step of applying a pretreatment agent to the fabric.
The pre-treatment step is performed in advance before printing so that the colorant ((A-1) phthalocyanine dye, (A-2) non-phthalocyanine dye, etc.) in the ink set is fixed to the cloth. In contrast, it is a step of applying a pretreatment agent containing a hydrotropic agent, an aqueous (water-soluble) metal salt, a pH adjuster, a pH buffer, a polymer component and the like.
In the pretreatment step, it is preferable to put the pretreatment agent within a range of 5% to 150%, preferably 10% to 130%. The pretreatment agent may further impart a water repellent, a surfactant and the like.

(Pretreatment agent)
-Hydrotropic agent-
In the present invention, the hydrotropic agent generally serves to increase the color density of the image when the fabric to which the ink set is applied is heated under steam. Examples of the hydrotropic agent usually include urea, alkylurea, ethyleneurea, propyleneurea, thiourea, guanidate, and tetraalkylammonium halide.

-Aqueous metal salt-
Examples of the aqueous (water-soluble) metal salt include compounds that form a typical ionic crystal and have a pH of 4 to 10, such as alkali metal and alkaline earth metal halides.
Representative examples of such compounds include NaCl, Na ₂ SO ₄ , KCl, and CH ₃ COONa for alkali metals, and examples of alkaline earth metals include CaCl ₂ and MgCl ₂ . Of these, Na, K, and Ca salts are preferred.

-PH adjuster-
Examples of the pH adjuster include alkali (base), acid, or a combination of alkali and acid. The pH adjuster refers to a compound or composition that adjusts the liquidity (pH) of the ink set (first and second ink compositions) applied to the fabric, and is a component that changes the liquidity of the ink set. Say. By containing the pH adjuster, the immobilization reaction of the colorant to the fabric can be enhanced.
The content of the pH adjusting agent with respect to the total mass of the pretreatment agent is less than 1% by mass, but is preferably 0% by mass.

-PH buffer-
Examples of the pH buffer include acid ammonium salts represented by ammonium sulfate, ammonium tartrate and the like. The pH buffering agent refers to a component that suppresses the liquid property change of the ink set (first and second ink compositions). The pH buffering agent can enhance the immobilization reaction of the colorant to the fabric, like the pH adjusting agent.

-Polymer component-
The polymer component may be a natural polymer or a synthetic polymer. Further, it may be an aqueous (water-soluble) polymer or a non-aqueous polymer, but since the ink set used in the printing method of the present invention is an aqueous composition, it is an aqueous polymer. Is preferred. By containing the polymer component, it is possible to provide a role as a paste for adhering the colorant to the fabric.
Examples of the aqueous polymer include starch substances such as corn and wheat, cellulosic substances such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, polysaccharides such as sodium alginate, arabic gum, locust bean gum, tant gum, guar gum, tamarind seed, gelatin And known natural aqueous polymers such as protein substances such as casein, tannin substances, and lignin substances.
Examples of the synthetic aqueous polymer include known polyvinyl alcohol compounds, polyethylene oxide compounds, acrylic acid aqueous polymers, and maleic anhydride aqueous polymers. Of these, polysaccharide polymers and cellulose polymers are preferred.

-Water repellent-
Examples of the water repellent include paraffinic compounds, fluorine compounds, pyridinium salts, N-methylol alkylamides, alkylethylene ureas, oxalin derivatives, silicone compounds, triazine compounds, zirconium compounds, or mixtures thereof. However, it is not particularly limited. Among these water repellents, paraffin-based and fluorine-based water repellents are particularly preferable in terms of prevention of bleeding and concentration.
The amount of the water repellent applied to the fabric is not particularly limited, but it is preferably applied in the range of 0.05% to 40% by mass with respect to the total mass of the fabric. This is because if the content is less than 0.05% by mass, the effect of preventing excessive penetration of the ink is small, and even if the content exceeds 40% by mass, there is no significant change in performance.
The amount of the water repellent used relative to the total mass of the fabric is more preferably in the range of 0.5 mass% to 10 mass%.

-Surfactant-
Examples of the surfactant that can be used as the pretreatment agent include anionic, nonionic, and amphoteric surfactants. In particular, a nonionic surfactant having an HLB of 12.5 or more is preferably used, and a nonionic surfactant having 14 or more is more preferably used.
A betaine type etc. can be used as an amphoteric surfactant.
The amount of the surfactant applied to the fabric is not particularly limited, but is preferably 0.01% by mass to 30% by mass with respect to the total mass of the fabric.

-Other ingredients-
The pretreatment agent may further contain additives such as a reducing agent, an antioxidant, a leveling agent, a deep dyeing agent, a carrier, a reducing agent, and an oxidizing agent depending on the characteristics of the dye used. .

The pretreatment agent may be applied to the fabric as a mixture in which various components such as the above-described hydrotropic agent, water repellent, and surfactant are mixed. For example, the hydrotropic agent may be used without mixing the various components. The first pretreatment agent containing only the first pretreatment agent and the second pretreatment agent containing only the water repellent agent may be prepared, and the respective pretreatment agents may be sequentially applied to the fabric.
When the pretreatment agent is a mixture of the various components described above, the content of the various components with respect to the total mass of the pretreatment agent that is the mixture is various when the pretreatment agent is applied to the fabric. What is necessary is just to adjust suitably according to the objective so that the provision amount of a component may become the range as stated above.

  In the pretreatment, the method for incorporating each of the above pretreatment agents into the fabric is not particularly limited, and examples thereof include a usual dipping method, pad method, coating method, spray method, and ink jet method.

[Drying process]
In the textile printing method of the present invention, after printing by applying an ink set (first and second ink compositions) to the fabric, the printed fabric is wound up, the fabric is heated to cause color development, and the fabric is washed. And drying.
In textile printing by the ink jet method, by following the above procedure, dyeing of (A-1) a phthalocyanine dye and (A-2) a non-phthalocyanine dye is compared with the case where the ink is applied as it is after the ink application process. Is sufficiently performed, the color density is high, and the water resistance is excellent. In particular, when printing is continued for a long time while transporting a long fabric with a roller or the like, the printed fabric will be transported endlessly, and the fabric printed on the floor will overlap. In addition to taking up space, it can be unsafe and dirty unexpectedly. Therefore, it is preferable to perform an operation of winding the printed fabric after printing. During this winding operation, a medium not related to printing, such as paper, cloth, or vinyl, may be sandwiched between the cloths. However, when the printed fabric is cut in the middle or when the printed fabric is short, it is not always necessary to wind it.

  Further, after the ink application step, the printed fabric is preferably subjected to a post-treatment step, whereby (A-1) phthalocyanine dye and (A-2) non-phthalocyanine dye are fixed to the fiber. Promoted. Thereafter, it is preferable to sufficiently remove the unfixed colorant, other components, and the pretreatment agent.

[Post-treatment process]
The post-processing process is divided into several processes.
The post-processing can be configured by, for example, performing a preliminary drying process, a steam process, a cleaning process, and a drying process in this order.

-Predrying process-
First, after the ink application step, the fabric to which each ink composition constituting the ink set is applied is allowed to stand at room temperature (for example, 25 ° C.) to 150 ° C. for 0.5 to 30 minutes, and the ink is preliminarily dried. Is preferred. This preliminary drying can improve the printing density and effectively prevent bleeding. The preliminary drying includes that the ink penetrates into the fabric.

  According to the textile printing method of the present invention, preliminary drying can be performed by heating in a continuous process. After the fabric is rolled and supplied to an inkjet printing machine and printed (printed and printed), it is dried using a drier before winding the printed fabric. The dryer may be directly connected to the printing machine or separated. The drying of the fabric in the dryer is preferably performed at normal temperature (for example, 25 ° C.) to 150 ° C. for 0.5 to 30 minutes. Moreover, as a preferable drying method, an air convection method, a heating roll direct attachment method, an irradiation method, etc. are mentioned.

-Steam process-
The steam process is a process of accelerating the immobilization of (A-1) phthalocyanine dye and (A-2) non-phthalocyanine dye on the cloth by exposing the cloth to which ink has been applied to saturated steam. is there.
According to the textile printing method of the present invention, it is preferable that the steam process in the post-treatment is changed in conditions, particularly in the time, depending on the type of fabric.
For example, when the fabric is wool, the time for the steam process is preferably 1 minute to 120 minutes, more preferably about 3 minutes to 90 minutes. When the fabric is silk, the time is preferably 1 minute to 40 minutes, more preferably about 3 minutes to 30 minutes. Furthermore, when the fabric is nylon, it is preferably about 1 minute to 90 minutes, more preferably about 3 minutes to 60 minutes.

-Washing process-
In this way, most of the ink composition applied to the fabric by the inkjet method is fixed to the fabric, but some of the colorant of the ink composition does not stain the fiber. It is preferable to wash away the colorant which does not dye. A conventionally known cleaning method can be employed to remove the colorant that is not dyed. For example, it is preferable to use water in the range of room temperature (for example, 25 ° C.) to 100 ° C. or hot water, or to use an anionic or nonionic soaping agent. If the uncolored colorant is not completely removed, good results may not be obtained in various water resistances such as washing fastness and sweat fastness.

-Drying process (drying after washing)-
After washing the fabric, it is preferable to perform a drying step. Drying can be carried out by squeezing or dehydrating the washed fabric, drying it, or drying it using a dryer, heat roll, iron or the like.

<Fabric>
Since the fabric printed with the ink set of the present invention (the fabric of the present invention) has a better balance of dyeing properties compared to the printing with an ink set comprising an ink composition using a conventional general-purpose phthalocyanine dye, A stained image having an excellent taste balance is provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

[Synthesis Example: Synthesis of Dye-2]
Intermediate 001C was synthesized by the method described in US Patent Publication No. 2012-238752. By stirring the intermediate 001C and 1 equivalent of 4-amino-2,2,6,6-tetramethylpiperidine in 10 times the amount of acetonitrile relative to the total amount of the reaction substrate, the precipitated crystals were collected by filtration. Intermediate 001A was obtained.

The protonated form (SO ₃ H form) of intermediate 001B was obtained by the method described in the literature (Negrimovsky, V. et al., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 104, p. 161-168). Obtained. The obtained protonated product is added with 1.1 equivalents of potassium acetate in 20 parts by weight of isopropyl alcohol with respect to the protonated product, heated and stirred, cooled to room temperature, and the precipitated crystals are collected by filtration. Intermediate 001B was obtained.
19.6 g of the intermediate 001B, 12.0 g of the intermediate 001A, 142 mL of diethylene glycol, 29.5 g of ammonium benzoate, and 3.56 g of anhydrous copper (II) chloride were mixed and stirred at 100 ° C. for 12 hours. . 12 mL of concentrated hydrochloric acid was added dropwise thereto, and the mixture was further stirred for 30 minutes. Then, 2.9 L of isopropyl alcohol was added, and the mixture was further stirred for 30 minutes. The precipitated crystals were collected by filtration. The obtained crystals were dissolved in 750 mL of water, and 1 M aqueous sodium hydroxide solution was added until the pH of the solution was 12. The obtained solution was passed through a column filled with a cation exchange resin (Na foam) and concentrated with an evaporator to obtain 20.5 g of dye-2 crystals.

[Synthesis Example: Synthesis of Dye-6]
3-Nitrophthalonitrile (8.7 g), 3-tert-butylphenol (7.5 g), potassium carbonate (13.8 g), and DMF (50 mL) were placed in a flask and stirred at 60 ° C. for 2 hours. . The obtained reaction liquid was added to water (250 mL), and the precipitated crystals were collected by filtration. This crystal was blown and dried at 50 ° C. to obtain 13.4 g of intermediate 001-1.
¹ H NMR: δ = 1.35 (s, 9H), 7.00-7.08 (m, 2H), 7.10 (dd, 1H), 7.42-7.48 (m, 2H), 7.53 (d, 1H), 7.56 (d, 1H ) 300 MHz in CDCl ₃

Next, Intermediate 001-1 (11 g) and chloroform (100 mL) were placed in a flask and stirred under ice cooling. Chlorosulfuric acid (10 g) was added thereto, and the mixture was stirred for 5 minutes and then stirred at room temperature for 120 minutes. The resulting reaction solution was added to ice (200 g). The resulting mixture was extracted with chloroform, and the collected organic layer was dried over sodium sulfate. The solvent was removed, and the obtained residue was purified by silica gel column chromatography (developing solution: chloroform / methanol = 3/1) to obtain 7.0 g of intermediate 001-2.
¹ H NMR: δ = 1.30 (s, 9H), 6.96 (dd, 1H), 7.17 (d, 1H), 7.45 (dd, 1H), 7.53 (dd, 1H), 7.60 (d, 1H), 7.94 ( d, 1H) 300 MHz in CDCl ₃

Subsequently, phthalonitrile (5.0 g), sodium acetate (1.35 g), triethyl orthoacetate (3.3 g) and diethylene glycol (17.5 g) were added to the flask and stirred at 110 ° C. for 30 minutes. . The temperature was lowered to 100 ° C., ammonium benzoate (3.9 g) and copper (II) chloride (0.47 g) were added, and the mixture was stirred for 11 hours. The temperature was lowered to 80 ° C., concentrated hydrochloric acid (1.55 mL) was added, and the mixture was stirred for 0.5 hr. Water (150 mL) was added here and stirred. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration. The crystals collected by filtration were dissolved in water (150 mL), and 1 M aqueous sodium hydroxide solution was added to this solution to adjust the pH to 10. The solution was dedusted with celite, 4 L of acetonitrile was added, and the precipitated crystals were collected by filtration. The crystal was air-dried to obtain 2.6 g of Dye-6.
Λmax of solution spectrum = 693 nm (MeOH)

[Dye-1 to Dye-7]
The structures of Dye-1 to Dye-7 used in Examples and Comparative Examples are shown below.

Here, the dye-5 is obtained by subjecting the dye-1 to ion exchange treatment, and the dye-4 is obtained by subjecting the dye-2 to ion exchange treatment.
Such ion exchange treatment was performed as follows.
That is, a cation-form cation exchange resin was treated with tetrabutylammonium chloride to prepare a tetrabutylammonium type ion-exchange resin.
Subsequently, the dye-1 (commercial dye: CI Direct Blue 87) was treated with a cationic form cation exchange resin, followed by treatment with the tetrabutylammonium ion exchange resin obtained earlier, thereby producing tetrabutyl. Ammonium salt type dye-5 was obtained.
Similarly, ion exchange was performed in the same manner except that the dye-1 was changed to the dye-2 to obtain a tetrabutylammonium salt type dye-4.
Similarly, ion exchange was performed in the same manner except that the dye-1 was changed to the dye-6 to prepare a tetrabutylammonium salt type dye-7.

[Example 1]
(Pretreatment agent preparation)
First, components having the following composition were mixed to obtain a pretreatment agent.
-Pretreatment agent-
・ Guar gum (manufactured by Nissho Co., Ltd., MEYPRO GUM NP) 2%
・ Urea (made by Wako Pure Chemical Industries, Ltd.) 5%
・ Ammonium sulfate (Wako Pure Chemical Industries, Ltd.) 4%
・ Water: 89%

(Production of textile for printing)
Subsequently, using the pre-treatment agent obtained above, the silk fabric was put at a drawing ratio of 90% to obtain a treated fabric.

(Preparation of first ink composition)
Ingredients other than bromonium salt are mixed according to the following composition, then bromonium salt is added, and the obtained liquid is filtered through a membrane filter having a pore size of 0.5 μm to obtain first ink compositions 101-109. It was.
-Dye listed in Table 1 below 5%
・ Chemical bromonium salts listed in Table 1 below ・ Amounts listed in Table 1 ・ Glycerin [Wako Pure Chemical Industries, Ltd.] 10%
(Aqueous organic solvent)
・ Triethylene glycol monobutyl ether: 10%
[Wako Pure Chemical Industries, Ltd.] (aqueous organic solvent)
・ Orphine E1010 (manufactured by Nissin Chemical) 1%
(Acetylene glycol surfactant)
・ Proxel XL2 (manufactured by Arch Chemicals) ・ ・ ・ 0.2%
(Preservative and antifungal agent)
・ EDTA-2Na (Dojindo Laboratories) 0.005%
(Chelating agent)
・ Water ・ ・ ・ Remaining amount

  The first ink compositions C01 to C03 for comparison were prepared in the same manner as the preparation of the first ink composition except that no bromonium salt was added.

  The structure of the cation [(1) -1, (1) -2, (2), (3), and (4)] in Table 1 is as follows.

(Preparation of second ink composition)
The second ink compositions 201 to 210 were obtained in the same manner as in the preparation of the first ink composition except that the dyes were changed to those shown in Table 2 below and no bromonium salt was added.

[Preparation of ink set]
The obtained first and second ink compositions were combined as shown in Tables 3 and 4 below to obtain an ink set.
Here, the ink set using 101 to 109 as the first ink composition is the ink set of the present invention, and the ink set using C01 to C03 as the first ink composition is the ink set of the comparative example. Become.

[Evaluation]
The obtained ink set was set in an ink jet printer (DMP-2381 manufactured by Dimatics) using the pretreated fabric, and the first ink composition and the second ink composition were used on the fabric using this printer. Each of these was ejected onto the same spot, a solid image of a 3 cm square with two colors mixed was printed, and the fabric was dried to obtain a printed matter.

(Evaluation of dyeing rate)
Using the printed matter obtained as described above, the dyeing rate of the first ink composition was evaluated by the following method.
First, after printing, the fabric before steam is placed in 10 mL of warm water at 40 ° C., and the dye is washed out by applying ultrasonic waves for 10 minutes. Measured with
On the other hand, as a steam process, the printed material was subjected to steam in saturated steam at 100 ° C. for 30 minutes to fix the colorant to the fibers of the fabric. The obtained post-steamed fabric was immersed in warm water of 10 mL and 40 ° C. as described above to wash out the dye by applying ultrasonic waves for 10 minutes, and the absorbance of the liquid from which the dye was washed out was measured with a spectrophotometer U-4100 (Hitachi Manufactured).
From the obtained absorbance, the (A-1) phthalocyanine dye amount contained in the first ink composition was determined, and the dyeing rate was calculated by the following formula. The calculated values are also shown in Table 3 below.
Dyeing rate = [(A-1) amount of phthalocyanine dye washed out from fabric after steam] / [(A-1) amount of phthalocyanine dye washed out from fabric before steam]

(Evaluation of color balance)
As a steam process, the printed matter (fabric after printing) obtained as described above was steamed in saturated steam at 100 ° C. for 30 minutes to fix the colorant to the fibers of the fabric.
Thereafter, the fabric was washed with cold water for 10 minutes and warm water at 60 ° C. for 5 minutes, and then dried to prepare a printed sample.
The mixed color printing sample of the obtained ink set was visually observed, and in the mixed color solid image, A when the cyan color was felt, B when the slight cyan color was felt, and the cyan color remained. The case where it was hardly felt was evaluated as C.
The results are shown in Table 4.

As is apparent from Table 3, the ink set of the example using the first ink composition containing a bromonium salt has a higher dyeing rate than the comparative example.
Further, as is apparent from Table 4, it can be seen that the ink set of the example using the first ink composition containing the bromonium salt has a better color balance than the comparative example.

[Example 2]
The first ink compositions 111 to 113 were changed in the same manner as the preparation of the first ink composition in Example 1 except that the dyes were changed to those shown in Table 5 below and no bromonium salt was added. And the 1st ink compositions C11-C13 for comparison were obtained.
Further, as the second ink composition, the second ink compositions 201 to 210 in Example 1 described above were used.

[Preparation of ink set]
The obtained first and second ink compositions were combined as shown in Tables 6 and 7 below to obtain an ink set.
Here, the ink set using 111 to 113 as the first ink composition is the ink set of the present invention, and the ink set using C11 to C13 as the first ink composition is the ink set of the comparative example. Become.

[Evaluation]
Using the obtained ink set, evaluation of the balance of dyeing property and color was performed in the same manner as in Example 1.
Table 6 shows the results of evaluation of dyeing properties, and Table 7 shows the results of evaluation of color balance.

As can be seen from Table 6, the ink set of the example using the first ink composition containing the (A-1) phthalocyanine dye having a tetrabutylammonium salt of a sulfo group had a dyeing rate as compared with the comparative example. Is high.
Further, as is apparent from Table 7, the ink set of the example using the first ink composition containing the (A-1) phthalocyanine dye having a tetrabutylammonium salt of a sulfo group was more colored than the comparative example. You can see that the taste balance is good.

Claims (6)

A first ink composition comprising a phthalocyanine acid dye having a phthalocyanine skeleton, at least one ion selected from the group of ions represented by the following general formulas (1) to (4), and water:
A second ink composition comprising a dye having a skeleton other than the phthalocyanine skeleton, and water;
An ink set used for printing a fabric containing at least polyamide-based fibers.

[In General Formula (1), R ^{11 to} R ¹⁴ are each independently a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or a tertiary alkyl group having 4 to 6 carbon atoms. Represents a group, and any two of R ^{11 to} R ¹⁴ may be bonded to each other to form a ring.
In General Formula (2), R ^{21 to} R ²⁵ are each independently a hydrogen atom, a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or 3 having 4 to 6 carbon atoms. Represents a secondary alkyl group, and any two of R ^{21 to} R ²⁵ may be bonded to each other to form a ring; R ²⁶ represents a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or a tertiary alkyl group having 4 to 6 carbon atoms.
In General Formula (3), R ^{31 to} R ³³ are each independently a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or a tertiary alkyl group having 4 to 6 carbon atoms. And any two of R ^{31 to} R ³³ may be bonded to each other to form a ring. L ¹ represents an alkylene group, —O—, —S—, —NR ³⁴ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ³⁵ —, —CONR ³⁶ —, —SiR ³⁷ ₂ —. , An arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these groups. Here, R ^{34 to} R ³⁷ each independently represents a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 3 to 20 carbon atoms, or a tertiary alkyl group having 4 to 20 carbon atoms.
In General Formula (4), R ^{41 to} R ⁴⁵ are each independently a hydrogen atom, a primary alkyl group having 1 to 6 carbon atoms, a secondary alkyl group having 3 to 6 carbon atoms, or 3 having 4 to 6 carbon atoms. Represents a secondary alkyl group, and any two of R ^{41 to} R ⁴⁵ may be bonded to each other to form a ring. L ² represents an alkylene group, —O—, —S—, —NR ⁴⁶ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ⁴⁷ —, —CONR ⁴⁸ —, —SiR ⁴⁹ ₂ —. , An arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these groups. Here, R ^{46 to} R ⁴⁹ each independently represent a primary alkyl group having 1 to 20 carbon atoms, a secondary alkyl group having 3 to 20 carbon atoms, or a tertiary alkyl group having 4 to 20 carbon atoms. ] The ink set according to claim 1, wherein the phthalocyanine acid dye in the first ink composition is a compound represented by the following general formula (P1) or (P2).

[In General Formula (P1), X ^{1 to} X ⁴ each independently represents an oxygen atom or a sulfur atom. R ^{1 to} R ⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. P ^{1 to} P ⁴ each independently represents an aromatic ring, and the aromatic ring is a halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, alkyl Oxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfo group Sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl Group, Sill group, an ionic hydrophilic group, a cyano group, a hydroxy group, a nitro group, an amino group, which may have a carbonyl group, and a substituent selected from carbonylamino group. n ¹ to n ⁴ each independently represents an integer of 0 to 4, and the sum of n ^{1 to} n ⁴ is at least 1. However, the structure of the general formula (P1) includes at least two ionic hydrophilic groups.
In General Formula (P2), Y ^{101 to} Y ¹¹² each independently represent —CH— or a nitrogen atom. ^However, the number of nitrogen atoms in each group of ^{Y 101 ~Y 104, Y 105 ~Y} 108, and ^Y 109 ^{to Y 112} is an integer of 0-2. R ¹⁰¹ represents a hydrogen atom, an oxygen radical (—O ·), a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and R ¹⁰² and R ¹⁰³ are each independently a carbon atom. A secondary alkyl group having 3 to 20 carbon atoms or a tertiary alkyl group having 4 to 20 carbon atoms is represented. Further, any one of R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring. L ¹⁰¹ represents an alkylene group, —O—, —S—, —NR ²⁰¹ —, —CO—, —SO ₂ —, —COO—, —SO ₂ NR ²⁰¹ —, —CONR ²⁰¹ —, —SiR ²⁰¹ ₂ —. , An arylene group, a divalent heterocyclic group, and a divalent linking group selected from a divalent group formed by combining at least two of these groups. R ²⁰¹ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. One bond of L ¹⁰¹ is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, and the other bond is tetraaza It is bonded to the tetraazaporphyrin skeleton at the position where either the α-position or β-position hydrogen atom of the 6-membered ring of the porphyrin skeleton is removed. SO ₃ M ¹⁰² is bonded to NR ¹⁰¹ R ¹⁰² R ¹⁰³ at a position where any hydrogen atom in R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ is removed, or is a 6-membered ring of a tetraazaporphyrin skeleton. It is bonded to the tetraazaporphyrin skeleton at a position where either the α-position or β-position hydrogen atom is removed . M ¹⁰¹ represents a copper atom, a zinc atom, a nickel atom, or a cobalt atom, and M ¹⁰² represents a hydrogen atom or a monovalent counter cation. n ¹⁰¹ and n ¹⁰³ each independently represent an integer of 1 or more. ] The dye having a skeleton other than the phthalocyanine skeleton in the second ink composition is an aryl or heteryl azo dye, azomethine dye, methine dye, quinone dye, quinophthalone dye, nitro dye, nitroso dye, acridine dye, acridinone dye, carbonium dyes, polymethine dyes, Lee Njigo dye, and an ink set according to claim 1 or claim 2 is at least one dye selected from the group consisting of thioindigo dyes. The dye having a skeleton other than the phthalocyanine skeleton in the second ink composition is at least one dye selected from the group consisting of compounds represented by the following general formulas (D1) to (D6). The ink set according to any one of claims 1 to 3.

[In General Formulas (D1) and (D2), A, B, and C each independently represent an aromatic group or a heterocyclic group. N is an integer of 1 or more. However, at least one — (SO ₃ M) is introduced into the aromatic group or heterocyclic group represented by A, B, and C. M represents a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ .
In General Formula (D3), R ^{301 to} R ³⁰⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. The R ³⁰⁵ to R ³¹⁷ each independently represent a group on the benzene ring, represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, or a phenoxy ^{group, R} 305 to R Any two of ³¹⁷ may be connected to form a ring. However, at least one of R ^{301 to} R ³¹⁷ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m1 represents an integer of 1 to 13.
In General Formula (D4), R ^{401 to} R ⁴⁰⁴ each independently represents an alkyl group, an aryl group, or a heteroaryl group. R ^{405 to} R ⁴¹⁵ each independently represent a group on the benzene ring, and may be a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, aryl group, heteroaryl group, alkoxy group, amino group, or phenoxy. Represents a group, and any two of R ^{405 to} R ⁴¹⁵ may be linked to form a ring. However, at least one of R ^{401 to} R ⁴¹⁵ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m2 represents an integer of 1 to 11.
In general formula (D5), R ^{501 to} R ⁵⁰⁶ each independently represents a group on the benzene ring, and are a hydrogen atom, a hydroxy group, an alkyl group that may have a substituent, an aryl group, a heteroaryl group, An alkoxy group, an amino group, or a phenoxy group is represented, and X ¹ and X ² each independently represent —NR ⁵⁰⁷ R ⁵⁰⁸ , —OR ⁵⁰⁹ , or a hydroxy group. Any ^two of R ^{501 to} R ⁵⁰⁶ , X ¹ and X ² may be linked to form a ring. However, at least one of R ^{501 to} R ⁵⁰⁶ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m3 represents an integer of 1 to 6. R ⁵⁰⁷ , R ⁵⁰⁸ , and R ⁵⁰⁹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
In General Formula (D6), R ⁶⁰¹ and R ⁶⁰² each independently represent an alkyl group, an aryl group, or a heteroaryl group. R ^{603 to} R ⁶⁰⁹ each independently represents a group on the benzene ring, and represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, or a phenoxy group, and R ^{603 to} R ⁶⁰³ Any two of ⁶⁰⁶ and any two of R ^{607 to} R ⁶⁰⁹ may be linked to form a ring. However, at least one of R ^{601 to} R ⁶⁰⁹ includes — (SO ₃ M). Here, M is a hydrogen atom, an alkali metal ion, or NH ₄ ⁺ , and m4 represents an integer of 1 to 7. ]   A printing method for dyeing a fabric containing polyamide fibers by an ink jet method using the ink set according to any one of claims 1 to 4.   A fabric printed by the ink set according to any one of claims 1 to 4.