JP2013010826A - Ink set and liquid droplet discharging device using this - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set with good dispersibility of pigment even in a case when pigment ink and dye ink are mixed.SOLUTION: This ink set includes first ink containing water, pigment and a first metal ion as a counter ion of the pigment; and second ink containing water, a dye expressed by general formula (1) and a second metal ion as a counter ion of the dye, where the limiting equivalent conductivity [S cm/eq] of the first metal ion is larger than that of the second metal ion. In formula, n is 0 or 1; the group A is a substituted heterocyclic group; the group B is a phenyl group or a naphthyl group which may be substituted; Rrepresents an alkyl group, carboxy group, alkoxycarbonyl group, phenyl group, etc.

Description

  The present invention relates to an ink set and a droplet discharge device using the ink set.

  Conventionally, inks containing pigments or dyes as colorants are known. A pigment ink containing a pigment as a color material is particularly preferably used for recording characters and the like from the viewpoint of less bleeding and good water resistance and light resistance. In addition, a dye ink containing a dye as a coloring material is particularly preferably used for recording an image or the like from the viewpoint that glossiness and color developability are good and the color is clear.

  When pigment ink and dye ink having the above characteristics are used in combination, the recording quality of both characters and images recorded on the recording medium is excellent. For these reasons, ink sets including both pigment inks and dye inks have been widely used in recent years.

  By the way, when an ink set including a pigment ink and a dye ink is applied to an ink jet recording apparatus, the pigment ink and the dye ink may be mixed on a nozzle surface having a nozzle hole for ejecting ink. In such a case, the dispersibility of the pigment in the pigment ink may be destroyed by the dye ink, and the pigment may aggregate. In particular, when the nozzle surface is cleaned by a wipe member provided for cleaning the nozzle surface, the nozzle holes are blocked by the aggregates of the pigment, and the ejection stability of the ink may be lowered. . In addition, there is a problem that the aggregate of the pigment adhering to the nozzle surface falls on the recording medium.

  In order to reduce such agglomeration of the pigment, Patent Document 1 describes that a polymer having a lactam structure is added to the dye ink. Patent Document 2 describes that the amount of counter ions (counter ions) contained in pigment ink and dye ink is specified.

JP 2010-84136 A JP 2006-2094 A

  However, in the above-described prior art, when the pigment ink and the dye ink are mixed, the dispersion and destruction of the pigment cannot be sufficiently suppressed, and the aggregation of the pigment may occur. In particular, when a dye ink containing a specific dye improved to improve characteristics such as weather resistance (for example, light resistance and gas resistance) is used, the dye ink and the pigment ink are mixed. In some cases, the dispersibility of the pigment was significantly reduced.

  An object of some embodiments of the present invention is to solve at least a part of the above-described problems, and even when pigment ink and dye ink are mixed, dispersibility of pigments contained in the pigment ink Is to provide a good ink set.

  The present invention can be realized as the following aspects or application examples.

[Application Example 1]
One aspect of the ink set according to the present invention is:
Water, a pigment and a first ink containing a first metal ion as a counter ion of the pigment;
Water, a dye represented by the following general formula (1), and a second ink containing a second metal ion as a counter ion of the dye;
Have
The ultimate equivalent conductivity [S · cm ² / eq] of the first metal ion described in (Condition 1) or (Condition 2) below is the second metal described in (Condition 3) or (Condition 4) below. It is larger than the ultimate equivalent conductivity [S · cm ² / eq] of ions.
(Condition 1) When the first metal ion is composed of a single metal ion, the ultimate equivalent conductivity of the first metal ion is the ultimate equivalent conductivity of the single metal ion (Condition 2) the first When the metal ions are composed of two or more kinds of metal ions, the ultimate equivalent conductivity of the first metal ions is the average ultimate equivalent conductivity of the two or more kinds of metal ions (Condition 3). When the ion is composed of a single metal ion, the ultimate equivalent conductivity of the second metal ion is the ultimate equivalent conductivity of the single metal ion (Condition 4). The second metal ion is a metal of two or more types. When it consists of ions, the ultimate equivalent conductivity of the second metal ion is the average ultimate equivalent conductivity of the two or more metal ions.

（式（２）中、Ｒ^５は、メルカプト基；またはヒドロキシ基、Ｃ１−Ｃ４アルコキシ基、ヒドロキシＣ１−Ｃ４アルコキシ基、スルホ基もしくはカルボキシ基で置換されていてもよいＣ１−Ｃ４アルキルチオ基を表す。） (In the formula (1), n is 0 or 1,
R ¹ represents a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C4 alkyl group optionally substituted with a C1-C8 alkoxycarbonyl group or a carboxy group; or a hydroxy group, a sulfo group, or a carboxy group. Represents a good phenyl group,
R ² , R ³ and R ⁴ are each independently a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a hydroxy group, a C1-C4 alkoxy group, A C1-C4 alkoxy group optionally substituted with a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; A C1-C4 alkylcarbonylamino group optionally substituted with a hydroxy group or a carboxy group; an N′-C1-C4 alkylureido group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; the benzene ring is a chlorine atom C1-C4 alkyl group, nitro group, sulfo group Is a phenylamino group optionally substituted with a carboxy group; a benzoylamino group optionally substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or the benzene ring is chlorine Each represents an atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a phenylsulfonylamino group optionally substituted with a carboxy group;
The group A is a substituted heterocyclic group represented by the following general formula (2) or the following general formula (3),

(In formula (2), R ⁵ represents a mercapto group; or a C1-C4 alkylthio group optionally substituted with a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group. .)

(In Formula (3), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; a C1-C4 alkyl group. A C1-C4 alkoxy group optionally substituted with a hydroxy group, a C1-C4 alkoxy group, a sulfo group or a carboxy group; a C1-C4 alkylsulfonyl group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; Or a phenylsulfonyl group in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group;
Group B is an optionally substituted phenyl or naphthyl group,
When group B is a substituted phenyl group, hydroxy group; sulfo group; carboxy group; C1-C4 alkyl group; C1-C4 alkoxy group; amino group; mono- or di-C1-C4 alkylamino group; acetylamino group; A benzoylamino group in which the ring is optionally substituted by a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group;
When group B is a substituted naphthyl group, from the group consisting of a hydroxy group; a sulfo group; a C1-C4 alkoxy group; and a phenylsulfonyloxy group in which the benzene ring may be substituted with a methyl group, a nitro group, or a chlorine atom; With selected substituents. )
According to the ink set of Application Example 1, the dispersibility of the pigment contained in the first ink is good even when the first ink and the second ink are mixed.

[Application Example 2]
In application example 1,
The first metal ion may be at least one of sodium ion and lithium ion.

[Application Example 3]
In application example 1 or application example 2,
The second metal ion may be at least one of potassium ion and sodium ion.

[Application Example 4]
In any one of Application Examples 1 to 3,
In the general formula (1), R ¹ is a carboxy group or an unsubstituted C1-C4 alkyl group, the R ² is a sulfo C1-C4 alkoxy group, and the R ³ is a hydrogen atom, a methyl group, or an ethyl group. be able to.

[Application Example 5]
In any one of Application Examples 1 to 4,
The group A is a substituted heterocyclic group represented by the general formula (3),
In the general formula (3), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, chlorine atom, carboxy group, sulfo group, nitro group, C1-C4 alkyl group, C1-C4 alkoxy group. , A C1-C4 alkylsulfonyl group.

[Application Example 6]
In any one of Application Examples 1 to 5,
The dye may be a compound represented by the following formula (4) or a salt thereof.

[Application Example 7]
One aspect of the droplet discharge device according to the present invention is:
An ink set comprising the first ink and the second ink according to any one of Application Examples 1 to 6, and
A nozzle surface having nozzle holes for discharging the first ink and the second ink;
A wipe member for wiping the nozzle surface;
Have

1 is a perspective view illustrating a configuration of a printer according to an embodiment of the present invention. Schematic which shows the arrangement | sequence of the nozzle provided in the inkjet head in embodiment of this invention. FIG. 2 is a partial cross-sectional view showing an internal configuration of the ink jet head in the embodiment of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below describes an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

  In the present invention, acidic functional groups such as a sulfo group and a carboxy group are represented in the form of a free acid unless otherwise specified.

  In the present invention, “Cv-Cw alkyl (group)” (v and w are each an integer) means an alkyl group containing v to w carbon atoms. For example, C1-C4 alkyl refers to an alkyl group containing 1-4 carbon atoms. The alkyl group may have a linear or branched structure unless otherwise specified.

  “Cv-Cw alkoxy (group)” (v and w are each an integer) means an alkoxy group containing v to w carbon atoms. For example, C1-C4 alkoxy refers to an alkoxy group containing 1-4 carbon atoms. The alkoxy group may have a linear or branched structure unless otherwise specified.

  “Cv-Cw alkylene (group)” (v and w are each an integer) means an alkylene group containing v to w carbon atoms. For example, C1-C4 alkylene refers to an alkylene group containing 1 to 4 carbon atoms. The alkylene group may have a linear or branched structure unless otherwise specified.

1. Ink Set According to an embodiment of the present invention, an ink set includes water, a pigment, a first ink containing a first metal ion as a counter ion of the pigment, water, a dye represented by the following general formula (1), and A second ink containing a second metal ion as a counter ion of the dye, and the equivalent equivalent conductivity [S · cm ^{2 of} the first metal ion described in (Condition 1) or (Condition 2) below: / Eq] is larger than the ultimate equivalent conductivity [S · cm ² / eq] of the second metal ion described in (Condition 3) or (Condition 4) below.
(Condition 1) When the first metal ion is composed of a single metal ion, the ultimate equivalent conductivity of the first metal ion is the ultimate equivalent conductivity of the single metal ion (Condition 2) the first When the metal ions are composed of two or more kinds of metal ions, the ultimate equivalent conductivity of the first metal ions is the average ultimate equivalent conductivity of the two or more kinds of metal ions (Condition 3). When the ion is composed of a single metal ion, the ultimate equivalent conductivity of the second metal ion is the ultimate equivalent conductivity of the single metal ion (Condition 4). The second metal ion is a metal of two or more types. In the case of consisting of ions, the ultimate equivalent conductivity of the second metal ion is the average ultimate equivalent conductivity of the two or more metal ions. The ultimate equivalent conductivity of the first metal ion is that of the second metal ion. More than the ultimate equivalent conductivity If it is larger, the dispersibility of the pigment contained in the first ink is less likely to deteriorate when the first ink and the second ink are mixed. Thereby, even when the ink set according to the present embodiment is used in a droplet discharge device to be described later, it is possible to reduce the occurrence of discharge failure due to nozzle clogging or the like. On the other hand, when the ultimate equivalent conductivity of the first metal ions is equal to or less than the ultimate equivalent conductivity of the second metal ions, the dispersion of the pigment contained in the first ink when the first ink and the second ink are mixed. In some cases, the properties of the pigments deteriorate and pigment aggregation occurs.

  The ultimate equivalent conductivity (S · cm 2 / eq) of a metal ion is an eigenvalue in an infinite dilution state and is known as a value defined by the law of ion independent movement. That is, in the law of independent ion transfer, the limiting molar conductivity of the electrolyte in an infinite dilution state is expressed as the sum of the limiting molar conductivity of cations and anions. The infinite dilution state does not mean that there is no electrolyte (ion), but the cation-anion distance in the solution is infinite, and the cation and the anion affect each other. It means not. The equivalent conductivity (S · cm 2 / eq) of a metal ion is obtained by dividing the ultimate molar conductivity (S · cm 2 / mol) of the metal ion by the valence of the metal ion.

The ultimate equivalent conductivity of metal ions is often known. Specifically, the ultimate equivalent conductivity (S · cm 2 / eq) at 25 ° C. is 73.5 potassium ions (K ⁺ ), sodium ions ( Na ⁺ ) is 50.1, and lithium ion (Li ⁺ ) is 38.7 (Electrochemical Association “Electrochemical Handbook 4th Edition”). The ultimate equivalent conductivity of metal ions can also be determined experimentally, and determined by measuring the change in equivalent conductivity concentration and extrapolating to zero concentration using an appropriate method. Can do.

  Further, when the first metal ion is composed of two or more kinds of metal ions, the ultimate equivalent conductivity of the first metal ion is set as an average ultimate equivalent conductivity. The average ultimate equivalent conductivity is an average value of the ultimate equivalent conductivity of metal ions contained in the ink as a counter ion of the pigment. For example, the average ultimate equivalent conductivity of m X ions and n Y ions is [(the ultimate equivalent conductivity of X ions) × m + (the ultimate equivalent conductivity of Y ions) × n] / (M + n). In addition, also when a 2nd metal ion consists of 2 or more types of metal ions, an average ultimate equivalent conductivity can be calculated | required similarly to a 1st metal ion.

  The reason why the relationship between the ultimate equivalent conductivity affects the aggregation of the pigment has not been clarified in detail, but is considered to be due to the following mechanism.

  For example, when the ultimate equivalent conductivity of the second metal ion is larger than the ultimate equivalent conductivity of the first metal ion, when the first ink and the second ink are mixed, the conductivity around the pigment particles is increased. Get higher. That is, the pigment particles are likely to encounter metal ions having a high ultimate equivalent conductivity. As a result, it is considered that the electric double layer around the pigment contracts, thereby reducing the interparticle distance between the pigment particles and causing aggregation of the pigment.

  On the other hand, when the ultimate equivalent conductivity of the second metal ions is smaller than the ultimate equivalent conductivity of the first metal ions, the conductivity around the pigment particles is unlikely to increase. For this reason, it is considered that the aggregation of the pigment is less likely to occur.

  The first ink includes a pigment and a metal salt of a first metal ion. Thereby, the dispersibility of the pigment is improved and the aggregation of the pigment is less likely to occur.

  The second ink includes a dye represented by the general formula (1) and a metal salt of a second metal ion. This improves the solubility of the dye.

1.1. First Ink The ink set according to the present embodiment has a first ink. Hereinafter, the components contained in the first ink will be described in detail.

1.1.1. Pigment The first ink contains a pigment. Known pigments can be used as the pigment, but self-dispersing pigments are preferred. Self-dispersing pigments are pigments that can be dispersed in an aqueous medium without a dispersant. Here, “dispersed in an aqueous medium without a dispersant” means a state in which the surface is stably present in an aqueous medium by a hydrophilic group on the surface without using a dispersant for dispersing the pigment. Say. When a self-dispersing pigment is used, the amount of dispersant used to disperse the pigment can be reduced, so that foaming of the ink due to the dispersant can be reduced, and an ink with good ejection stability can be easily prepared.

Self-dispersing pigments can have hydrophilic groups on the pigment surface. Hydrophilic group of the surface of the _{pigment, -OM, -COOM, -CO -,} - SO 3 M, -SO 2 M, -SO 2 NH 2, -RSO 2 M, -PO 3 HM, -PO 3 M 2, - SO ₂ NHCOR, —NH ₃ , and —NR ₃ (wherein M is a hydrogen atom, an alkali metal (eg, lithium, sodium, potassium), ammonium, an optionally substituted phenyl group, or organic It represents ammonium, and R is preferably one or more hydrophilic groups selected from the group consisting of an alkyl group having 1 to 12 carbon atoms or a naphthyl group which may have a substituent.

  The first ink according to the present embodiment preferably includes a pigment and a metal salt of a first metal ion, and the pigment included in the first ink substantially includes a metal salt of the first metal ion. As described above, when the pigment contained in the first ink has a metal salt structure, the dispersibility of the pigment is improved and aggregation of the pigment is less likely to occur.

  The first metal ion contained in the first ink as the counter ion of the pigment is preferably at least one of potassium ion and sodium ion. Thereby, the dispersibility of the pigment in the first ink can be improved.

  The pigment is produced, for example, by bonding (grafting) the hydrophilic group to the surface of the pigment by performing physical treatment or chemical treatment. Examples of the physical treatment include vacuum plasma treatment. Examples of the chemical treatment include a wet oxidation method of oxidizing with an oxidizing agent in water, a method of binding a carboxyl group via a phenyl group by binding p-aminobenzoic acid to the pigment surface, and the like.

  When the first ink is used as a black ink (hereinafter also referred to as “pigment black ink”), the pigment is oxidized with hypohalous acid and / or hypohalite, oxidized with ozone, Or it is preferable that it is surface-treated by oxidation treatment with persulfuric acid and / or persulfate in terms of high color development.

  When the first ink is used as an ink of a color other than black (hereinafter also referred to as “pigment color ink”), the pigment may have the above hydrophilic group via a phenyl group on the surface thereof. From the viewpoint of high color development. As the surface treatment means for bonding a hydrophilic group to the pigment surface via a phenyl group, various known surface treatment means can be applied, and sulfanilic acid, p-aminobenzoic acid, 4-aminosalicylic acid and the like can be applied to the pigment surface. Examples thereof include a method of bonding a hydrophilic group via a phenyl group.

  As the pigment used in the pigment black ink, for example, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Preferred specific examples of carbon black include No. 2300, 900, MCF88, no. 20B, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, No2200B (manufactured by Mitsubishi Chemical Corporation), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex 30, U, V, 140U, special black 6, 5, 4A, 4, 250 (above Evonik Degussa), Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700 (above Colombia Carbon), Regal 400R, 330R, 660R, Mogul L , Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12 (manufactured by Cabot Corporation), and the like. These carbon blacks may be used alone or as a mixture of two or more.

  In addition, pigments used for pigment color inks include pigment red, pigment violet, pigment blue and the like described in the color index, as well as phthalocyanine, azo, anthraquinone, azomethine, condensed ring systems, etc. A pigment can be illustrated. In addition, organic pigments such as orange No. 228, 405, blue No. 1 and 404, and inorganic pigments such as titanium oxide, zinc oxide, zirconium oxide, iron oxide, ultramarine blue, bitumen, and chromium oxide can be mentioned. For example, C.I. I. Pigment red 1,3,5,8,9,16,17,19,22,38,57: 1,90,112,122,123,127,146,184, C.I. I. Pigment Bio Red 1,3,5: 1, 16, 19, 23, 38, C.I. I. And CI pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, and 16.

  Moreover, it is also possible to use a commercial item as a pigment, for example, microjet CW1 (made by Orient Chemical Industry Co., Ltd.), CAB-O-JET250C, CAB-O-JET260M (above made by Cabot Corporation), and the like. .

  The content of the pigment is preferably 1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less, with respect to the total mass of the first ink composition.

  The pigment preferably has an average particle size in the range of 50 to 250 nm from the viewpoint of storage stability of the ink and prevention of nozzle clogging.

1.1.2. Water The ink composition according to the present embodiment contains water. Water functions as a main solvent for dispersing or dissolving the above-described pigment.

  The water is preferably water from which ionic impurities such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water are removed as much as possible. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, it is preferable because the generation of mold and bacteria can be prevented when the pigment dispersion and the ink using the same are stored for a long period of time.

  The water contained in the first ink according to the present embodiment is preferably 50% by mass or more with respect to the total mass of the first ink.

1.1.3. Other Components The first ink according to the present embodiment can contain a surfactant. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Surfactant may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Among these, nonionic surfactants can improve the permeability and fixability of the ink to the recording medium, and the shape of the ink droplets deposited on the recording medium by the ink jet recording method is close to a perfect circle. Since it can be used, it can be preferably used.

  Among nonionic surfactants, acetylene glycol surfactants are more preferably used because they are excellent in ability to maintain surface tension and interfacial tension appropriately and have almost no foaming property. be able to. Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, or 3 , 5-dimethyl-1-hexyn-3-ol, 2,4-dimethyl-5-hexyn-3-ol, and the like. Commercially available acetylene glycol surfactants can also be used, such as Surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA (all are trade names, manufactured by Air Products and Chemicals Inc.), Olphin B, Y, P, A, STG, SPC , E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.).

  When the surfactant is contained, the content thereof is preferably 0.1% by mass or more and 5% by mass or less with respect to the total mass of the first ink.

  The first ink according to the present embodiment can contain a penetration enhancer. The penetration enhancer has an action of further improving the wettability of the ink with respect to the recording medium and applying it uniformly. As a result, it is possible to further reduce the density unevenness and bleeding of the ink of the formed image, and to further improve the color density of the image. A penetration enhancer may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Examples of the penetration enhancer include glycol ethers. Glycol ethers are particularly excellent in effect as penetration enhancers. Examples of glycol ethers include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol. And monobutyl ether. Among these, triethylene glycol monobutyl ether can be preferably used from the viewpoint of excellent compatibility with the components contained in the first ink according to the present embodiment.

  When the penetration accelerator is contained, the content thereof is preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the first ink.

  The first ink according to the present embodiment can contain a humectant. Examples of the humectant include 1,2-alkanediols, polyhydric alcohols, pyrrolidone derivatives, ureas, and the like. A moisturizer may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Since 1,2-alkanediols are excellent in the action of increasing the wettability of the ink to the recording medium and uniformly wetting it, an excellent image can be formed on the recording medium. Examples of 1,2-alkanediols include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, and the like. . When 1,2-alkanediols are contained, the content thereof is preferably 1% by mass or more and 20% by mass or less with respect to the total mass of the first ink.

  Polyhydric alcohols can be preferably used from the viewpoint that when the first ink is used in an ink jet recording apparatus, clogging or ejection failure can be reduced by suppressing drying and solidification of the ink on the nozzle surface of the head. . Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, Examples include glycerin. When polyhydric alcohols are contained, the content thereof is preferably 1% by mass or more and 30% by mass or less with respect to the total mass of the first ink.

  The pyrrolidone derivative can be preferably used from the viewpoint of suppressing clogging and ejection failure by suppressing drying and solidification of the ink on the nozzle surface of the head. Examples of pyrrolidone derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. Etc. When the pyrrolidone derivative is contained, the content thereof is preferably 1% by mass or more and 10% by mass or less with respect to the total mass of the first ink.

  Ureas can be preferably used from the viewpoint that when the first ink is used in an ink jet recording apparatus, clogging or ejection failure can be reduced by suppressing drying and solidification of the ink on the nozzle surface of the head. Examples of ureas include urea, thiourea, ethylene urea, 1,3-dimethylimidazolidinone and the like. When urea is contained, the content thereof is preferably 1% by mass or more and 20% by mass or less with respect to the total mass of the first ink.

  The 1st ink which concerns on this embodiment can contain a pH adjuster. The pH adjuster can easily adjust the pH value of the first ink. A pH adjuster may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Examples of pH adjusters include inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid), inorganic bases (for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia), organic bases (triethanolamine, diethanolamine, mono Ethanolamine, tri-iso-propanolamine), organic acids (for example, adipic acid, citric acid, succinic acid, etc.) and the like.

  Among the above, it is preferable to use at least one of an organic acid and an organic base as the pH adjuster. In particular, when an organic acid and an organic base are used in combination, the pH buffering ability is higher than that of a combination of an inorganic acid and an inorganic base, an inorganic acid and an organic base, or an organic acid and an inorganic base. Therefore, when an organic acid and an organic base are used in combination, the effect of suppressing fluctuations in pH value is further improved, and the effect of being easily set to a desired pH is achieved.

  The 1st ink which concerns on this embodiment can contain antiseptic | preservative and antifungal agent, a rust preventive agent, a chelating agent, etc. further. If the first ink according to the present embodiment contains these compounds, the characteristics may be further improved.

  Examples of antiseptics and fungicides include sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline-3-one Etc. Examples of commercially available products include Proxel XL2, Proxel GXL (above trade name, manufactured by Avicia), Denside CSA, NS-500W (above trade name, manufactured by Nagase ChemteX Corporation), and the like.

  Examples of the rust inhibitor include benzotriazole.

  Examples of the chelating agent include ethylenediaminetetraacetic acid and salts thereof (such as ethylenediaminetetraacetic acid dihydrogen disodium salt).

1.2. Second Ink The ink set according to the present embodiment has a second ink. In the second ink, components other than the pigment among the components contained in the first ink described above can be used in the same manner, and thus the description of the components used in the same manner is omitted.

1.2.1. Dye (a) Dye The second ink according to this embodiment comprises a dye represented by the following general formula (1) (hereinafter also referred to as “first dye”) and a second metal ion as a counter ion of the dye. contains.

  The first dye has the property of not easily decomposing even when irradiated with light or exposed to atmospheric gas (especially ozone). Therefore, an image formed using the second ink is excellent in light resistance and gas resistance (particularly ozone resistance), and hardly undergoes discoloration or fading due to the influence of light or air. Further, the first dye has a property that it is difficult to decompose in the ink. Therefore, the second ink is excellent in storage stability.

  The content of the first dye is preferably 1% by mass to 15% by mass and more preferably 1% by mass to 10% by mass with respect to the total mass of the second ink. When the content of the first dye is within the above range, the color density of the recorded image can be improved, and the light resistance and gas resistance can be improved.

In the general formula (1), n is 0 or 1, and R ¹ is a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C8 alkoxycarbonyl group or a C1-C4 optionally substituted with a carboxy group. An alkyl group; or a phenyl group optionally substituted by a hydroxy group, a sulfo group or a carboxy group.

R ² , R ³ and R ⁴ each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a hydroxy group, or a C1-C4 alkoxy group. Group, a hydroxy C1-C4 alkoxy group, a C1-C4 alkoxy group optionally substituted with a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino optionally substituted with a hydroxy group, a sulfo group or a carboxy group A C1-C4 alkylcarbonylamino group which may be substituted with a hydroxy group or a carboxy group; an N′-C1-C4 alkylureido group which may be substituted with a hydroxy group, a sulfo group or a carboxy group; Chlorine atom, C1-C4 alkyl group, nitro group, sulfo Or a phenylamino group optionally substituted with a carboxy group; a benzene ring in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring in chlorine Each represents an atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a phenylsulfonylamino group optionally substituted with a carboxy group.

  The group A is a substituted heterocyclic group represented by the following general formula (2) or the following general formula (3).

In the general formula (2), R ⁵ represents a mercapto group; or a C1-C4 alkylthio group optionally substituted with a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group. Represent.

In the general formula (3), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; Group: C1-C4 alkoxy group optionally substituted with a hydroxy group, C1-C4 alkoxy group, sulfo group or carboxy group; C1-C4 alkylsulfonyl group optionally substituted with a hydroxy group, sulfo group or carboxy group Or a phenylsulfonyl group in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group, respectively.

  The group B is an optionally substituted phenyl group or naphthyl group. In addition, when group B is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group; an amino group; a mono- or di-C1-C4 alkylamino group; And a benzene ring having a substituent selected from the group consisting of a benzoylamino group optionally substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group. On the other hand, when the group B is a substituted naphthyl group, it comprises: a hydroxy group; a sulfo group; a C1-C4 alkoxy group; and a phenylsulfonyloxy group in which the benzene ring may be substituted with a methyl group, a nitro group, or a chlorine atom; Having a substituent selected from the group.

  The first dye is a compound having a tautomer. Examples of tautomers include compounds represented by the following general formulas (5) to (7), and these tautomers can also be used as the first dye according to the present embodiment.

In the above general formulas (5) to (7), n, R ¹ , R ² , R ³ , R ⁴ , group A and group B have the same meaning as in general formula (1).

In the general formula (1), R ¹ is a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C8 alkoxycarbonyl group or a C1-C4 alkyl group optionally substituted with a carboxy group; or a hydroxy group, a sulfo group, or It represents a phenyl group which may be substituted with a carboxy group.

When R ¹ in the general formula (1) is a C1-C8 alkoxycarbonyl group, the alkoxycarbonyl group may be any of linear, branched and alkyl moieties having a cyclic structure. The alkoxycarbonyl group is preferable. Specific examples include straight chain such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl and the like; A branched chain such as isopropoxycarbonyl, isobutyloxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, 2,2-dimethylpropoxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, 2-methylbutyloxycarbonyl; Alkyl moieties such as methyloxycarbonyl, cyclobutylmethyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl have a cyclic structure. Shall; and the like. Among these, a linear C1-C6 alkoxycarbonyl group is more preferable, and a linear C1-C4 alkoxycarbonyl group is more preferable.

When R ¹ in the general formula (1) is a C1-C4 alkyl group which may be substituted with a C1-C8 alkoxycarbonyl group or a carboxy group, and the C1-C4 alkyl group is an unsubstituted C1-C4 alkyl group, The alkyl group may be linear or branched, but is preferably linear. Specific examples of the C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl. Further, when the C1-C4 alkyl group has a substituent, the alkyl group includes those exemplified in the case where the C1-C4 alkyl group is an unsubstituted C1-C4 alkyl group, and preferable ones. It can be the same. When the substituent of the C1-C4 alkyl group is a C1-C8 alkoxycarbonyl group, the alkoxycarbonyl group may be the same as the case where R ¹ is a C1-C8 alkoxycarbonyl group, including preferable ones. When R ¹ is a C1-C4 alkyl group substituted with a C1-C8 alkoxycarbonyl group, preferred specific examples include methoxycarbonylmethyl, ethoxycarbonylethyl, n-butoxycarbonylmethyl, n-octyloxycarboxyethyl and the like. It is done. When R ¹ is a C1-C4 alkyl group which may be substituted with a carboxy group, preferred specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and the like.

Specific examples when R ¹ in the general formula (1) is a phenyl group which may be substituted with a hydroxy group, a sulfo group or a carboxy group include, for example, unsubstituted phenyl; 2-hydroxyphenyl, 4-hydroxy Hydroxy-substituted phenyl such as phenyl; sulfo-substituted phenyl such as 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl; 2-carboxyphenyl, 4-carboxyphenyl, 3, Carboxy-substituted phenyl such as 5-dicarboxyphenyl; and phenyl substituted with a plurality of groups such as 2-hydroxy-5-sulfophenyl; and the like.

Among the above, R ¹ in the general formula (1) is more preferably a carboxy group; a C1-C4 alkoxycarbonyl group; an unsubstituted C1-C4 alkyl group; a carboxy group-substituted C1-C4 alkyl group; or an unsubstituted phenyl group. Specific examples of preferable R ¹ in the general formula (1) include methyl, ethyl, tert-butyl, carboxymethyl, 3-carboxypropyl, methoxycarbonylmethyl, carboxy, methoxycarboxy, ethoxycarboxy, n-octyloxycarboxy, phenyl 2-hydroxyphenyl and 4-sulfophenylmethyl, more preferably methyl, carboxymethyl, carboxy and phenyl, still more preferably methyl and carboxy.

In the general formula (1), R ² , R ³ and R ⁴ each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, C1-C4 alkoxy group optionally substituted with a sulfo group or a carboxy group; mono- or di-optionally substituted with a hydroxy group, a sulfo group or a carboxy group C1-C4 alkylamino group; C1-C4 alkylcarbonylamino group optionally substituted with hydroxy group or carboxy group; N′-C1-C4 alkylureido optionally substituted with hydroxy group, sulfo group or carboxy group Group: the benzene ring is a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group A phenylamino group optionally substituted by a group or a carboxy group; a benzoylamino group optionally substituted by a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring A phenylsulfonylamino group which may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group;

When R ^{2 to} R ⁴ in the general formula (1) are an unsubstituted C1-C4 alkoxy group, the alkoxy group may be linear or branched. Specific examples of the unsubstituted C1-C4 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like. When the alkoxy group is substituted with a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, 2-hydroxyethoxy, 2-hydroxypropoxy, Hydroxy C1-C4 alkoxy groups such as 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n- C1-C4 alkoxy C1-C4 alkoxy group such as propoxybutoxy; Hydroxy C1-C4 alkoxy C1-C4 alkoxy group such as 2-hydroxyethoxyethoxy; 3-sulfopropoxy, 4-sulfobut Sulfo C1-C4 alkoxy group sheet like; carboxymethoxy, 2-carboxyethoxy, carboxy C1-C4 alkoxy group such as a 3-carboxypropoxy; and the like.

When R ^{2 to} R ⁴ in the general formula (1) are an unsubstituted mono- or di-C1-C4 alkylamino group, the C1-C4 alkyl moiety may be linear or branched. Specific examples of the unsubstituted mono- or di-C1-C4 alkylamino group include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di- -Straight chain such as n-butylamino; branched chain such as sec-butylamino, tert-butylamino, diisopropylamino; and the like. When the mono- or di-C1-C4 alkylamino group is substituted with a hydroxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, 2-hydroxyethylamino, 2-hydroxypropylamino, 2,2 Hydroxy-substituted mono- or di-C1-C4 alkylamino groups such as'-dihydroxydiethylamino; sulfo-substitutions such as 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3,3'-disulfodipropylamino Mono- or di-C1-C4 alkylamino group; carboxy-substituted mono- or di-C1-C4 alkylamino group such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethylamino; Can be mentioned.

When R ^{2 to} R ⁴ in the general formula (1) are an unsubstituted C1-C4 alkylcarbonylamino group, the C1-C4 alkyl moiety may be either linear or branched, but is linear Is preferred. Specific examples of the unsubstituted C1-C4 alkylcarbonylamino group include acetylamino, propanoylamino, butanoylamino and the like. When the C1-C4 alkylcarbonylamino group is substituted with a hydroxy group or a carboxy group, specific examples of the C1-C4 alkylcarbonylamino group include, for example, hydroxyethanoylamino, 2-hydroxypropanoylamino, A hydroxy C1-C4 alkylcarbonylamino group such as 4-hydroxybutanoylamino; a carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropanoylamino; and the like.

When R < ² > -R < ⁴ > in General formula (1) is a N'-C1-C4 alkylureido group, the direction which has a substituent is more preferable than an unsubstituted thing. When the N′-C1-C4 alkylureido group is substituted with a hydroxy group, a sulfo group or a carboxy group, specific examples thereof include N′-2-hydroxyethylureido and N′-3-hydroxyethyl. N′-hydroxy C1-C4 alkylureido group such as ureido; N′-sulfoC1-C4 alkylureido group such as N′-2-sulfoethylureido, N′-3-sulfopropylureido; N′-carboxymethylureido N′-2-carboxyethylureido, N′-3-carboxypropylureido, N′-4-carboxybutylureido, and other N′-carboxyC1-C4 alkylureido groups;

Specific examples of the phenylamino group in which R ^{2 to} R ⁴ in the general formula (1) may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group include, for example, Unsubstituted phenylamino; Chlorine atom substituted phenylamino groups such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, 4-tert-butylphenylamino, etc. C1-C4 alkyl-substituted phenylamino group; 2-nitrophenylamino, nitro-substituted phenylamino groups such as 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, Sulfo-substituted phenyla such as 3,5-disulfophenylamino Amino group; 2-carboxyphenyl-amino, 4-carboxyphenyl amino, 2,5-carboxyphenyl amino, 3,5-dicarboxyphenyl carboxy-substituted phenylamino group phenylamino and the like; and the like.

R ^{2 to} R ⁴ in the general formula (1) are a phenylamino group, a benzoylamino group or a phenylsulfonylamino group having a substituent, and the substituent of the benzene ring contained in each group is a C1-C4 alkyl group. In some cases, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples of the alkyl group include, for example, straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl.

Specific examples of the benzoylamino group in which R ^{2 to} R ⁴ in the general formula (1) may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group include, for example, Unsubstituted benzoylamino; chlorine-substituted benzoylamino groups such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; 2-methylbenzoylamino, 3-methylbenzoylamino, 4-methylbenzoylamino, etc. C1-C4 alkyl-substituted benzoylamino group; 2-nitrobenzoylamino, 4-nitrobenzoylamino, nitro-substituted benzoylamino groups such as 3,5-dinitrobenzoylamino; 2-sulfobenzoylamino, 4-sulfobenzoylamino, etc. Sulfo-substituted benzoylamino group; 2 Carboxy benzoylamino, 4-carboxyphenyl benzoylamino, 3,5-carboxymethyl benzoyl carboxy-substituted benzoylamino group of the amino or the like; and the like.

Specific examples of the phenylsulfonylamino group in which R ^{2 to} R ⁴ in the general formula (1) may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group include, for example, Unsubstituted phenylsulfonylamino; chlorine atom-substituted phenylsulfonylamino groups such as 2-chlorophenylsulfonylamino, 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, 4-tert-butylphenylsulfonylamino A C1-C4 alkyl-substituted phenylsulfonylamino group such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, 4-nitrophenylsulfonylamino and the like; 3-sulfophenyl Sulfonylamino, 4-sulfophenyl sulfonyl sulfo-substituted phenylsulfonylamino group of the amino or the like; 3-carboxyphenyl sulfonylamino, 4-carboxyphenyl sulfonyl carboxy-substituted phenylsulfonylamino group of the amino or the like; and the like.

Specific examples of preferable R ^{2 to} R ⁴ in the general formula (1) are a hydrogen atom, carboxy, sulfo, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfo. Butoxy, carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2′- Dihydroxydiethylamino, 2,2′-dicarboxydiethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, 4-hydroxybutanoylamino, N′-carboxymethylureido, N′- 2-sulfoethylureido, -Sulfophenylamino, 2,4-disulfophenylamino, 2,5-dicarboxyphenylamino, benzoylamino, 3-sulfobenzoylamino, 2-carboxybenzoylamino, phenylsulfonylamino, 4-methylphenylsulfonylamino, 4 -Nitrophenylsulfonylamino, 3-sulfophenylsulfonylamino, 4-carboxyphenylsulfonylamino and the like, more preferably hydrogen atom, sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy 4-sulfobutoxy, dimethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, N′-2-sulfoethylureido, 2,4-disulfophenylamino, benzoyla Roh, 4-methyl-phenylsulfonylamino, more preferably a hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy.

In a preferable combination of R ^{2 to} R ⁴ in the general formula (1), R ² is 3-sulfopropoxy or 4-sulfobutoxy, R ³ is a hydrogen atom, and R ⁴ is methyl.

When R ⁵ in the general formula (2) is a C1-C4 alkylthio group, the C1-C4 alkyl moiety is preferably linear or branched, but more preferably linear. Specific examples of the C1-C4 alkylthio group include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio and the like. In addition, when R ⁵ in the general formula (2) is a C1-C4 alkylthio group having a substituent, the substituent is preferably a hydroxy group, a sulfo group or a carboxy group, and is a sulfo group or a carboxy group. Is more preferable. Specific examples of the substituted C1-C4 alkylthio group include, for example, hydroxy C1-C4 alkylthio groups such as 2-hydroxyethylthio, 2-hydroxypropoxy, 3-hydroxypropoxythio; methoxyethylthio, ethoxyethylthio, C1-C4 alkoxy C1-C4 such as n-propoxyethylthio, isopropoxyethylthio, n-butoxyethylthio, methoxypropylthio, ethoxypropylthio, n-propoxypropylthio, isopropoxybutylthio, n-propoxypropylthio Alkylthio group; hydroxy C1-C4 alkoxy C1-C4 alkylthio group such as 2-hydroxyethoxyethylthio; sulfo C1-C4 alkylthio group such as 3-sulfopropylthio, 4-sulfobutylthio; carboxymethylthio 2-carboxyethyl thio, carboxy C1-C4 alkylthio group such as 3-carboxypropyl thio; and the like.

Specific examples of preferable R ⁵ in the general formula (2) are mercapto (—SH), methylthio, ethylthio, 2-hydroxyethylthio, methoxyethylthio, ethoxyethylthio, 2-sulfoethylthio-3-sulfopropylthio, 4- Sulfobutylthio, carboxymethylthio, 2-carboxyethylthio, 3-carboxypropylthio and the like, more preferably methylthio, 2-sulfopropylthio, carboxymethylthio, 2-carboxyethylthio, and still more preferably 2- Sulfopropylthio and 2-carboxyethylthio.

When R ^{6 to} R ⁸ in the general formula (3) are a C1-C4 alkyl group, the alkyl group may be linear, branched or cyclic, but is linear or branched It is preferable that it is linear. Specific examples of the C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

When R ^{6 to} R ⁸ in the general formula (3) are a C1-C4 alkoxy group which may be substituted with a hydroxy group, a C1-C4 alkoxy group, a sulfo group or a carboxy group, the substituent is preferable. And R ^{2 to} R ⁴ in the general formula (1) may be the same as those in the case of a C1-C4 alkoxy group.

Specific examples of the C1-C4 alkylsulfonyl group in which R ^{6 to} R ⁸ in the general formula (3) may be substituted with a hydroxy group, a sulfo group, or a carboxy group include, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, Linear or branched C1-C4 alkylsulfonyl groups such as isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl; hydroxy C1-C4 alkyl such as 2-hydroxyethylsulfonyl and 3-hydroxypropylsulfonyl A sulfonyl group; a sulfo C1-C4 alkylsulfonyl group such as 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl, 4-sulfobutylsulfonyl; carboxymethylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxy Carboxy C1-C4 alkylsulfonyl group such as a ball propyl sulfonyl; and the like.

Specific examples of the phenylsulfonyl group in which R ^{6 to} R ⁸ in the general formula (3) may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group include, for example, Unsubstituted phenylsulfonyl; chlorine atom-substituted phenylsulfonyl groups such as 2-chlorophenylsulfonyl and 4-chlorophenylsulfonyl; 2-methylphenylsulfonyl, 4-methylphenylsulfonyl, 2,4-dimethylphenylsulfonyl, 4-tert-butylphenylsulfonyl C1-C4 alkyl-substituted phenylsulfonyl groups such as 2-nitrophenylsulfonyl, 4-nitrophenylsulfonyl and the like nitro-substituted phenylsulfonyl groups; 3-sulfophenylsulfonyl, 4-sulfophenylsulfonyl, 3,5-disulfophenylsulfur Sulfo-substituted phenylsulfonyl group such as sulfonyl; 2-carboxyphenyl sulfonyl, 4-carboxyphenyl sulfonyl, 3,5-carboxyphenyl carboxy-substituted phenylsulfonyl group such as phenylsulfonyl; and the like.

Specific examples of preferable R ^{6 to} R ⁸ in the general formula (3) include a hydrogen atom, a chlorine atom, carboxy, sulfo, nitro, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, and 3-sulfo. Propoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, methylsulfonyl, ethylsulfonyl, tert-butylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, phenylsulfonyl, 4-chlorophenyl Sulfonyl, 4-methylphenylsulfonyl, 2,4-dimethylphenylsulfonyl, 4-nitrophenylsulfonyl, 4-sulfophenylsulfonyl, 2-carboxyphenylsulfonyl, 4-carboxyphenylsulfonyl By weight, more preferably, a hydrogen atom, a chlorine atom, carboxy, sulfo, nitro, methyl, methoxy, methylsulfonyl, 2-carboxyphenyl sulfonyl, more preferably a hydrogen atom, sulfo, methoxy. In addition, at least one of R ^{6 to} R ⁸ is preferably a hydrogen atom, and at least one is preferably a substituent other than a hydrogen atom.

A preferable combination of R ⁶ , R ⁷ and R ⁸ in the general formula (3) is a hydrogen atom, methoxy and sulfo, or one is sulfo and the other two are hydrogen atoms. When one is sulfo and the other two are hydrogen atoms, the substitution position of sulfo is more preferably the 6-position of the benzothiazole ring.

  In the general formula (1), the group B is an optionally substituted phenyl group or naphthyl group. When the group B is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; -C4 alkoxy group; amino group; mono- or di-C1-C4 alkylamino group; acetylamino group; benzoyl optionally substituted on the benzene ring with a chlorine atom, C1-C4 alkyl group, nitro group, sulfo group or carboxy group An amino group having a substituent selected from the group consisting of a hydroxy group in the case of a substituted naphthyl group; a sulfo group; a C1-C4 alkoxy group; a benzene ring substituted with a methyl group, a nitro group or a chlorine atom; Or a phenylsulfonyloxy group having a substituent selected from the group consisting of:

In the case where the group B in the general formula (1) is a phenyl group or a naphthyl group having a substituent, and the substituent is a C1-C4 alkoxy group, the alkoxy group includes a preferable one. It may be the same as the case where R ^{2 to} R ⁴ are an unsubstituted C1-C4 alkoxy group.

When the group B in the general formula (1) is a mono- or di-C1-C4 alkylamino group-substituted phenyl group, the mono- or di-C1-C4 alkylamino group includes R ^{2 in the} general formula (1) including preferable ones. It may be the same as when R ⁴ is an unsubstituted mono- or di-C1-C4 alkylamino group.

  When the group B in the general formula (1) is a substituted naphthyl group, and the substituent is a phenylsulfonyloxy group in which the benzene ring may be substituted with a methyl group, a nitro group, or a chlorine atom, as specific examples thereof, For example, unsubstituted phenylsulfonyloxy; methyl-substituted phenylsulfonyloxy groups such as 4-methylphenylsulfonyloxy and 2,4-dimethylphenylsulfonyloxy; nitro-substituted phenylsulfonyl such as 2-nitrophenylsulfonyloxy and 4-nitrosulfonyloxy An oxy group; a chlorine atom-substituted phenylsulfonyloxy group such as 4-chlorophenylsulfonyloxy, 2,4-dichlorophenylsulfonyloxy, 3,5-dichlorophenylsulfonyloxy; and the like.

  In general formula (1), n is preferably 1.

  Specific examples of preferred substituents when the group B in the general formula (1) is a substituted phenyl group include a hydrogen atom, hydroxy, sulfo, carboxy, methyl, ethyl, methoxy, ethoxy, dimethylamino, acetylamino, benzoylamino, 4-sulfobenzoylamino, 4-carboxybenzoylamino, and the like, more preferably a hydrogen atom, hydroxy, sulfo, carboxy, methyl, and acetylamino, and still more preferably a hydrogen atom, sulfo, and carboxy.

  Specific examples of preferred substituents when the group B in the general formula (1) is a substituted naphthyl group are hydrogen atom, hydroxy, sulfo, methoxy, ethoxy, phenylsulfonyloxy, 4-methylphenylsulfonyloxy, 2-nitrophenyl. And more preferably a hydrogen atom, hydroxy, sulfo, and methoxy, and more preferably a hydrogen atom and sulfo.

  Specific examples of preferable group B in the general formula (1) include phenyl, 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, 4-carboxyphenyl, 3,5 -Carboxyphenyl, 4-methylphenyl, 3-methylphenyl, 3-hydroxy-4-carboxyphenyl, 5-sulfo-3-carboxy-2-hydroxyphenyl, 4-methoxyphenyl, 4-acetylaminophenyl, naphthyl, naphtho -2-yl, 6-sulfonaphthyl, 7-sulfonaphthyl, 4,7-disulfonaphthyl, 5,7-disulfonaphth-2-yl, 6,8-disulfonaphth-2-yl, 4,8-disulfonaphtho-2 -Yl, 4,6,8-trisulfonaphth-2-yl and the like, more preferably phenyl, 4-sulfopheny 2,4-disulfophenyl, 4-carboxyphenyl, 3,5-carboxyphenyl, 5,7-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl, and more preferably phenyl, 4-sulfophenyl, 4-carboxyphenyl, and 3,5-carboxyphenyl.

The compound which combined the preferable thing described about the substituent of General formula (1)-(3) and General formula (5)-(7) is more preferable, The compound which combined more preferable things is further more preferable. . The same applies to the case where more preferable ones are combined. Incidentally, as described above, the general formula (5) ⁿ in ~ ^(7), R 1 to R ^4, group A and group B are as defined in formula (1).

  The dye represented by the general formula (1) can form a salt by utilizing a sulfo group in the molecule. When forming a salt, the sulfo group in the molecule preferably forms a salt with each cation such as a metal, ammonia or an organic base.

  Examples of the metal include alkali metals and alkaline earth metals. Examples of the alkali metal include lithium, sodium, potassium and the like. Examples of the alkaline earth metal include calcium and magnesium.

  Examples of the organic base include quaternary ammonium ions represented by the following general formula (8), but are not limited thereto.

  The second ink according to this embodiment includes a dye represented by the general formula (1) and a metal salt of a second metal ion, and the dye contained in the second ink is substantially composed of a metal salt of the second metal ion. It is preferable to become. This is because the solubility of the dye is improved.

  The second metal ion contained in the second ink as the counter ion of the first dye is preferably at least one of sodium ion and lithium ion. Thereby, the solubility of the first dye in the second ink can be improved.

  Moreover, a mixture may be sufficient as the free acid of the 1st dye which concerns on this embodiment, its tautomer, and those various salts. For example, a mixture of the sodium salt of the first dye and the ammonium salt of the first dye, a mixture of the free acid of the first dye and the sodium salt of the first dye, the lithium salt of the first dye, the sodium salt of the first dye, and Any combination such as a mixture of ammonium salts of the first dye may be used. Depending on the type of salt, the physical properties such as solubility may differ, so it is possible to select the type of salt as necessary or change the ratio when multiple salts are included. A mixture having physical properties suitable for the above can be obtained.

In the general formula (8), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group.

Specific examples of the alkyl group of Z ¹ , Z ² , Z ³ , Z ^{4 in} the general formula (8) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Is mentioned. Specific examples of the hydroxyalkyl group include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl and 2-hydroxybutyl. Can be mentioned. Examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl. An isohydroxy C1-C4 alkoxy C1-C4 alkyl group may be mentioned. Among these, hydrogen atom, methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like can be preferably used.

Specific examples of preferred combinations of Z ¹ , Z ² , Z ³ and Z ^{4 for} the quaternary ammonium ion represented by the formula (8) are shown in Table 1.

  Although it does not specifically limit as a suitable specific example of a 1st dye, The compound etc. which are represented by the structural formula shown in Table 2-Table 7 are mentioned. In each table, functional groups such as sulfo groups and carboxy groups are described in the form of free acids for convenience.

(B) Dye synthesis method The first dye can be synthesized, for example, by the following method. In addition, the structural formula of the compound in each process shall be represented in the form of a free acid for convenience.

  First, a compound represented by the following general formula (9) is diazotized by a conventional method, and this and a compound represented by the following general formula (10) are subjected to a coupling reaction by a conventional method and represented by the following general formula (11). To obtain a compound. Next, after diazotizing the obtained compound of the general formula (11) by a conventional method, this and a compound represented by the following general formula (12) are subjected to a coupling reaction by a conventional method, and the following general formula (13) To obtain a compound represented by: And after diazotizing the compound of the obtained general formula (13) by a conventional method, this and the compound represented by the following general formula (14) are made a coupling reaction by a conventional method, General formula (1) The 1st dye which concerns on this embodiment represented by these can be obtained. In addition, the compound represented by General formula (14) can purchase a commercial item as a product, or is compoundable by a well-known method.

  The diazotization of the compound of the following general formula (9) is carried out by a known method. For example, the diazotization of the compound of the following general formula (9) is carried out using nitrosylsulfuric acid in sulfuric acid, acetic acid or phosphoric acid, for example at a temperature of -5 ° C to 20 ° C, preferably 5 ° C to 10 ° C. Further, the coupling of the diazotized compound of the compound of the general formula (9) and the compound of the general formula (10) is carried out under known conditions. Specifically, the coupling between the diazotized compound of the compound of the general formula (9) and the compound of the general formula (10) is, for example, -5 ° C to 30 ° C, preferably 10 ° C to 30 ° C in water or an aqueous organic medium. It is carried out at a temperature of ° C. The compound of the general formula (9) and the compound of the general formula (10) can be used in almost stoichiometric amounts.

  The diazotization of the compound of the general formula (11) is performed by a known method. Specifically, the diazotization of the compound of the general formula (12) is carried out in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example -5. It is carried out using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -40 ° C, preferably 5-30 ° C. Moreover, the coupling of the diazotized compound of the compound of the general formula (11) and the compound of the general formula (12) is carried out under known conditions. Specifically, the coupling of the diazotized compound of the compound of the general formula (11) and the compound of the general formula (12) is performed in water or an aqueous organic medium, for example, -5 ° C to 50 ° C, preferably 10 ° C to 30 ° C. It is preferable to carry out the reaction at a slightly acidic to alkaline pH value. The coupling of the diazotized compound of the general formula (11) and the compound of the general formula (12) is more preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6 to pH 10. Since the diazotization reaction solution is acidic, the reaction system is further acidified due to the progress of the coupling reaction. Therefore, it is preferable to adjust the pH value by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compounds of general formula (11) and general formula (12) can be used in approximately stoichiometric amounts.

  The diazotization of the compound of the general formula (13) is performed by a known method. Specifically, the diazotization of the compound of the general formula (13) is performed in water or an aqueous organic medium (a mixture of water and a water-soluble organic solvent, etc.) in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid, for example, It is carried out using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of 5 ° C to 40 ° C, preferably 10 ° C to 30 ° C. Further, the coupling of the diazotized compound of the compound of the general formula (13) and the compound of the general formula (14) is performed under known conditions. The coupling of the diazotized compound of the compound of the general formula (13) and the compound of the general formula (14) is carried out in water or an aqueous organic medium, for example, at a temperature of -5 ° C to 50 ° C, preferably 10 ° C to 30 ° C. It is preferable to carry out at a weakly acidic to alkaline pH value. The coupling of the diazotized compound of the compound of the general formula (13) and the compound of the general formula (14) is more preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6 to pH10. It is preferable to carry out by addition. As a base, the thing similar to what was used by the coupling of the diazo compound of the compound of General formula (11) and the compound of General formula (12) can be used. The compounds of general formulas (13) and (14) can be used in approximately stoichiometric amounts.

  In order to make the dye of the general formula (1) into a desired salt, it is salted out by adding a desired inorganic salt or organic cation salt to the reaction solution after the coupling reaction, or a mineral acid such as hydrochloric acid. Is added in the form of the free acid and washed with water, acidic water or an aqueous organic medium as necessary to remove the inorganic salt, and then the desired inorganic base or By neutralizing with an organic base, a corresponding salt solution can be obtained.

  As an example, a method for converting the dye represented by the general formula (1) into a lithium salt will be described below. After coupling reaction of the compound of general formula (13) and the compound of general formula (14), sodium chloride is added, salting out and filtration are performed, whereby the dye represented by general formula (1) The sodium salt of is obtained. Next, water and hydrochloric acid are added to the sodium salt, and acid precipitation and filtration are performed to obtain a free acid of the dye represented by the general formula (1). Furthermore, the lithium salt of the dye represented by the general formula (1) can be obtained by adding water and lithium hydroxide to the free acid. Moreover, as a different method to make a lithium salt, a salt exchange reaction using a sodium salt of a dye represented by the general formula (1) and lithium chloride can be mentioned.

  In addition, acidic water means what acidified by dissolving organic acids, such as mineral acids, such as a sulfuric acid and hydrochloric acid, and an acetic acid, in water. The aqueous organic medium refers to water-miscible organic substances miscible with water and so-called organic solvents miscible with water. Specific examples of the aqueous organic medium include water-soluble organic solvents and the like, but even organic substances that are not usually classified as solvents can be used as needed as long as they are miscible with water. .

  Examples of the water-soluble organic solvent include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol; carvone such as N, N-dimethylformamide or N, N-dimethylacetamide. Acid amides; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone or N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2 -Cyclic ureas such as -one; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2-propylene glycol, 1,3- Lopylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol or dithio Mono-, oligo- or poly-alkylene glycols or thioglycols having C2-C6 alkylene units such as diglycol; polyols (triols) such as glycerin or hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (Butyl carbitol) C1-C4 alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; .gamma.-butyrolactone or dimethyl sulfoxide and the like.

  Examples of organic substances that are not usually classified as solvents include urea and saccharides. Examples of the inorganic salt include alkali metal salts such as lithium chloride, sodium chloride and potassium chloride, and ammonium salts such as ammonium chloride and ammonium bromide. Examples of the organic cation salt include a halogen salt of an organic amine. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Can be mentioned. Examples of the organic base include organic amines such as quaternary ammoniums represented by the general formula (8) such as diethanolamine and triethanolamine, but are not limited thereto.

一般式（９）中、基Ａは、式（２）および式（３）におけるものと同じ意味を表す。

In general formula (9), group A represents the same meaning as in formula (2) and formula (3).

一般式（１０）中、Ｒ^２、Ｒ^３およびＲ^４は、式（１）におけるものと同じ意味を表す。

In general formula (10), R ² , R ³ and R ⁴ represent the same meaning as in formula (1).

一般式（１１）中、基Ａ、Ｒ^２、Ｒ^３およびＲ^４は、式（１）〜式（３）におけるものと同じ意味を表す。

In general formula (11), groups A, R ² , R ³ and R ⁴ represent the same meaning as in formulas (1) to (3).

一般式（１２）中、ｎは、式（１）におけるものと同じ意味を表す。

In general formula (12), n represents the same meaning as in formula (1).

一般式（１３）中、Ｒ^２、Ｒ^３およびＲ^４は、式（１）におけるものと同じ意味を表す。

In general formula (13), R ² , R ³ and R ⁴ represent the same meaning as in formula (1).

一般式（１４）中、Ｒ^１および基Ｂは、式（１）におけるものと同じ意味を表す。

In general formula (14), R ¹ and group B represent the same meaning as in formula (1).

  Among the compounds shown in Tables 2 to 7, the first dye is compound No. 14 or a salt thereof, and compound No. 14 A compound represented by the following general formula (4) or a salt thereof, which is a mixture of the compound represented by 22 or a salt thereof, can be preferably used.

1.3. Physical Properties of Each Ink When the ink set according to the present embodiment is used in an ink jet recording apparatus, the viscosity of each ink (first ink and second ink) at 20 ° C. is 2 mPa · s or more and 10 mPa · s or less, respectively. It is preferably 3 mPa · s or more and 6 mPa · s or less. If the viscosity at 20 ° C. is within the above range, each ink can be suitably used in an ink jet recording apparatus because it is ejected in an appropriate amount from the nozzle and can further reduce the occurrence of flight bending and scattering. The viscosity of each ink can be measured by maintaining the temperature of the ink at 20 ° C. using a vibration viscometer VM-100AL (manufactured by Yamaichi Electronics Co., Ltd.).

2. Droplet Discharge Device A droplet discharge device according to an embodiment of the present invention includes the above-described ink set including the first ink and the second ink, and a nozzle hole for discharging the first ink and the second ink. It has a nozzle surface and a wipe member for wiping the nozzle surface.

  Hereinafter, a droplet discharge device according to an embodiment of the present invention will be described with reference to FIGS. In each drawing used for the following description, the scale of each member is appropriately changed to make each member a recognizable size. In this embodiment, an ink jet printer (hereinafter simply referred to as “printer”) is exemplified as the droplet discharge device according to the present invention.

  FIG. 1 is a perspective view illustrating a configuration of a printer 1 according to the present embodiment. The printer 1 represents a serial printer.

  As shown in FIG. 1, a printer 1 includes an inkjet head 2 and a carriage 4 on which an ink cartridge 3 is detachably mounted, and a platen 5 disposed below the inkjet head 2 and to which a recording medium 6 is conveyed. And a carriage moving mechanism 7 for moving the carriage 4 in the medium width direction of the recording medium 6 and a medium feeding mechanism 8 for conveying the recording medium 6 in the medium feeding direction. In addition, the printer 1 includes a control device CONT that controls the operation of the entire printer 1. The medium width direction is the main scanning direction (head scanning direction). The medium feeding direction is a sub-scanning direction (a direction orthogonal to the main scanning direction).

  The ink cartridge 3 is not limited to the one mounted on the carriage 4 as in the present embodiment, but instead, for example, a type that is mounted on the housing side of the printer 1 and is supplied to the inkjet head 2 via the ink supply tube. It may be. The ink cartridge 3 contains a first ink, a second ink, a third ink, and a fourth ink, respectively. The ink set of the printer 1 includes a first ink, a second ink, a third ink, and a fourth ink. The third ink and the fourth ink may be an ink having the same composition as at least one of the first ink and the second ink, or may be an ink having a composition different from that of the first ink and the second ink.

  The carriage 4 is attached in a state of being supported by a guide rod 9 which is a support member installed in the main scanning direction. The carriage 4 is moved in the main scanning direction along the guide rod 9 by the carriage moving mechanism 7.

  The linear encoder 10 detects the position of the carriage 4 in the main scanning direction with a signal. This detected signal is transmitted to the control device CONT as position information. The control device CONT recognizes the scanning position of the ink jet head 2 based on the position information from the linear encoder 10 and controls the recording operation (discharge operation) and the like by the ink jet head 2. Further, the control device CONT is configured to be able to variably control the moving speed of the carriage 4.

  FIG. 2 is a schematic diagram showing the arrangement of the nozzle holes 17 provided in the inkjet head 2 in the present embodiment.

  As shown in FIG. 2, the ink jet head 2 has a nozzle surface 21A provided with a plurality of nozzle holes 17 for ejecting ink. A nozzle row 16 is formed for each of the plurality of nozzle holes 17 on the nozzle surface 21 </ b> A which is also an ink ejection surface. In each nozzle row 16, for example, inks having different compositions can be ejected. In the present embodiment, four rows corresponding to the ink composition, that is, the nozzle row 16 (first ink), the nozzle row 16 (second ink), the nozzle row 16 (third ink), and the nozzle row 16 (fourth ink). ) Is provided. Each nozzle row 16 is configured by, for example, 180 nozzle holes 17.

  FIG. 3 is a partial cross-sectional view showing the internal configuration of the inkjet head 2 in the present embodiment.

  As shown in FIG. 3, the inkjet head 2 includes a head main body 18 and a flow path forming unit 22 connected to the head main body 18. The flow path forming unit 22 includes a vibration plate 19, a flow path substrate 20, and a nozzle substrate 21, and forms a common ink chamber 29, an ink supply port 30, and a pressure chamber 31. Furthermore, the flow path forming unit 22 includes an island portion 32 that functions as a diaphragm portion, and a compliance portion 33 that absorbs pressure fluctuation in the common ink chamber 29. In the head main body 18, an accommodation space 23 for accommodating the drive unit 24 together with the fixing member 26 and an internal flow path 28 for guiding ink to the flow path forming unit 22 are formed.

  According to the above configuration, that is, the piezo-type inkjet head 2, when a drive signal is input to the drive unit 24 via the cable 27, the piezoelectric element 25 expands and contracts. As a result, the diaphragm 19 is deformed (moved) in a direction toward and away from the pressure chamber 31. For this reason, the volume of the pressure chamber 31 changes and the pressure of the pressure chamber 31 containing ink fluctuates. Ink is ejected from the nozzle hole 17 due to the fluctuation of the pressure.

  Returning to FIG. 1, a home position serving as a scanning start point of the inkjet head 2 is set in a region outside the platen 5 in the movement range of the inkjet head 2. A maintenance unit 11 is provided at the home position. The maintenance unit 11 performs a moisturizing operation for capping the ink jet head 2 with the cap member 12 other than the printing operation to suppress ink evaporation, and preliminarily ejecting the ink to the cap member 12 from each nozzle hole 17 of the ink jet head 2. Prevention of clogging of the nozzle hole 17 with thickened ink, adjustment of the meniscus of the nozzle hole 17 to normally discharge ink from the inkjet head 2, and suction (not shown) after the inkjet head 2 is capped with the cap member 12. A suction operation (head cleaning) for normally ejecting ink from the ink-jet head 2 by adjusting the meniscus by forcibly sucking ink with increased viscosity or adhering dust from each nozzle hole 17 by driving the pump; Nozzle of head 2 21A (see FIG. 2) is wiped with the wiping member 13 to remove ink adhering to the nozzle hole 17 or thickened ink, or to destroy the meniscus in the nozzle hole 17 and readjust the meniscus. And a wiping operation for performing the purge process.

  The first ink and the second ink have the above-described composition. For this reason, even if the first ink and the second ink are mixed on the nozzle surface 21A by wiping, the aggregation of the pigment is less likely to occur, so that the clogging of the nozzle holes 17 due to the aggregation of the pigment can be reduced. As a result, the printer 1 has good ejection stability.

3. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

3.1. Ink preparation 3.1.1. Preparation of Pigment Ink (1) Preparation of Pigment Dispersion Add 20 parts by mass of black pigment and 80 parts by mass of ion-exchanged water as a pigment, and after mixing and stirring, using a sand mill (manufactured by Yaskawa Seisakusho Co., Ltd.), zirconia beads (A diameter of 1.5 mm) and a dispersion treatment were performed for 6 hours. Then, the pigment dispersion liquid was obtained by isolate | separating a zirconia bead with a separator.

(2) Preparation of Pigment Ink Next, components were mixed and stirred at the blending amounts shown in Table 8, and pressure filtration was performed with a membrane filter having a pore size of 10 μm to obtain pigment ink A and pigment ink B. In addition, the unit described in Table 8 is mass%.

  Further, the viscosity of each pigment ink was measured by maintaining the temperature of the ink at 20 ° C. using a vibration viscometer VM-100AL (manufactured by Yamaichi Electronics Co., Ltd.). The viscosity of each pigment ink is also shown in Table 8.

3.1.2. Preparation of dye ink Each component was mixed and stirred at the blending amounts shown in Table 8 and subjected to pressure filtration with a membrane filter having a pore size of 1.0 μm to obtain dye ink A, dye ink B, dye ink C, dye ink D and Dye ink E was obtained.

  Moreover, the viscosity of each dye ink was measured by maintaining the temperature of the ink at 20 ° C. using a vibration viscometer VM-100AL (manufactured by Yamaichi Electronics Co., Ltd.). The viscosity of each dye ink is also shown in Table 24.

In addition, each component in Table 8 is as follows. As the black pigment A, a product obtained by treating a product name Printex 30 manufactured by Evonik Degussa Co., Ltd. according to a conventional method to form a potassium salt was used. Moreover, the black pigment B used the thing made into the sodium salt by processing Ebonic Degussa Co., Ltd. product name Printex 30 by the conventional method. Moreover, the dye A-dye E used what processed the compound represented by following formula (4) by the conventional method, and was used as the salt.
(Pigment)
・ Black pigment A (potassium salt)
・ Black pigment B (sodium salt)
(dye)
Dye A (lithium salt of a compound represented by the following formula (4))
Dye B (sodium salt of the compound represented by the following formula (4))
Dye C (potassium salt of the compound represented by the following formula (4))
Dye D (mixed salt of lithium salt and sodium salt of the compound represented by the above formula (4); Li: Na = 8: 2)
Dye E (mixed salt of lithium salt and potassium salt of the compound represented by the above formula (4); Li: K = 5: 5)
(Penetration enhancer)
・ Triethylene glycol monobutyl ether (humectant)
・ 1,2-Hexanediol ・ Glycerin ・ Triethylene glycol ・ Trimethylolpropane ・ 2-Pyrrolidone (surfactant)
-Acetylene glycol surfactant A (trade name “Orphine E1010”, manufactured by Nissin Chemical Industry Co., Ltd.)
Acetylene glycol surfactant B (trade name “Surfinol 104”, manufactured by Air Products and Chemicals Inc.)
(PH adjuster)
・ Triethanolamine ・ Potassium hydroxide (water)
・ Ion exchange water

3.2. Evaluation test 3.2.1. Measurement of conductivity The conductivity at 20 ° C. of each pigment ink and each dye ink was measured by a conductivity meter DS-52 (trade name, HORIBA, Ltd.). The measurement results are also shown in Table 8.

3.2.2. Evaluation of ejection stability Each pigment ink and each dye ink were filled in a nozzle row of an inkjet printer PX-B500 (trade name, manufactured by Seiko Epson Corporation). Of these inks, one type of pigment ink and one type of dye ink are selected, (a) check printing using the selected pigment ink and dye ink, and (b) nozzle surface suction operation (head cleaning). The nozzle surface wiping, (c) check printing using the selected pigment ink and dye ink, and (d) leaving the ink jet printer for 24 hours were performed 10 cycles in this order. .

Thereafter, the selected pigment ink and dye ink were ejected from the nozzles, check printing was performed, and the ejection stability was evaluated by confirming the presence or absence of nozzle omission and ink flight bending. The evaluation results are shown in Table 25. The classification of evaluation criteria is as follows.
“○”: No nozzle missing or ink flying bent “×”: No nozzle missing or ink flying bent

3.3. Evaluation results Table 9 shows the results of the above evaluation tests.

  In each of the ink sets of Examples 1 to 4 in Table 9, the ultimate equivalent conductivity of the metal ion (first metal ion) contained in the pigment ink is the ultimate equivalent of the metal ion (second metal ion) contained in the dye ink. Greater than conductivity. Therefore, the discharge stability test showed that there were no nozzle omissions or flight bends. As a result, it was shown that even when the pigment ink and the dye ink are mixed, aggregation of the pigment hardly occurs.

  On the other hand, in each of the ink sets of Comparative Examples 1 to 4 in Table 9, the ultimate equivalent conductivity of the metal ion (first metal ion) contained in the pigment ink is that of the metal ion (second metal ion) contained in the dye ink. Below the equivalent equivalent conductivity. For this reason, in the discharge stability test, nozzle missing and flight bending occurred. Thus, it was shown that pigment aggregation occurred due to the mixing of the pigment ink and the dye ink. In addition, the aggregation of the pigment occurred frequently when the nozzle surface was wiped, and also occurred when the splashes of the dye ink adhered to the nozzle holes for discharging the pigment ink when the dye ink was discharged.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 1 ... Printer, 2 ... Inkjet head, 3 ... Ink cartridge, 4 ... Carriage, 5 ... Platen, 6 ... Recording medium, 7 ... Carriage moving mechanism, 8 ... Medium feed mechanism, 9 ... Guide rod, 10 ... Linear encoder, DESCRIPTION OF SYMBOLS 11 ... Maintenance unit, 12 ... Cap member, 13 ... Wipe member, 16 ... Nozzle row, 17 ... Nozzle hole, 18 ... Head body, 19 ... Vibration plate, 20 ... Flow path substrate, 21 ... Nozzle substrate, 21A ... Nozzle surface , 22 ... flow path forming unit, 23 ... accommodating space, 24 ... drive unit, 25 ... piezoelectric element, 26 ... fixing member, 27 ... cable, 28 ... internal flow path, 29 ... common ink chamber, 30 ... ink supply port, 31 ... Pressure chamber, 32 ... Island part, 33 ... Compliance part, CONT ... Control device

Claims (7)

Water, a pigment and a first ink containing a first metal ion as a counter ion of the pigment;
Water, a dye represented by the following general formula (1), and a second ink containing a second metal ion as a counter ion of the dye;
Have
The ultimate equivalent conductivity [S · cm ² / eq] of the first metal ion described in (Condition 1) or (Condition 2) below is the second metal described in (Condition 3) or (Condition 4) below. An ink set that is larger than the ultimate equivalent conductivity [S · cm ² / eq] of ions.
(Condition 1) When the first metal ion is composed of a single metal ion, the ultimate equivalent conductivity of the first metal ion is the ultimate equivalent conductivity of the single metal ion (Condition 2) the first When the metal ions are composed of two or more kinds of metal ions, the ultimate equivalent conductivity of the first metal ions is the average ultimate equivalent conductivity of the two or more kinds of metal ions (Condition 3). When the ion is composed of a single metal ion, the ultimate equivalent conductivity of the second metal ion is the ultimate equivalent conductivity of the single metal ion (Condition 4). The second metal ion is a metal of two or more types. When it consists of ions, the ultimate equivalent conductivity of the second metal ion is the average ultimate equivalent conductivity of the two or more metal ions.

(In the formula (1), n is 0 or 1,
R ¹ represents a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C4 alkyl group optionally substituted with a C1-C8 alkoxycarbonyl group or a carboxy group; or a hydroxy group, a sulfo group, or a carboxy group. Represents a good phenyl group,
R ² , R ³ and R ⁴ are each independently a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a hydroxy group, a C1-C4 alkoxy group, A C1-C4 alkoxy group optionally substituted with a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; A C1-C4 alkylcarbonylamino group optionally substituted with a hydroxy group or a carboxy group; an N′-C1-C4 alkylureido group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; the benzene ring is a chlorine atom C1-C4 alkyl group, nitro group, sulfo group Is a phenylamino group optionally substituted with a carboxy group; a benzoylamino group optionally substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or the benzene ring is chlorine Each represents an atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a phenylsulfonylamino group optionally substituted with a carboxy group;
The group A is a substituted heterocyclic group represented by the following general formula (2) or the following general formula (3),

(In formula (2), R ⁵ represents a mercapto group; or a C1-C4 alkylthio group optionally substituted with a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group. .)

(In Formula (3), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; a C1-C4 alkyl group. A C1-C4 alkoxy group optionally substituted with a hydroxy group, a C1-C4 alkoxy group, a sulfo group or a carboxy group; a C1-C4 alkylsulfonyl group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; Or a phenylsulfonyl group in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group;
Group B is an optionally substituted phenyl or naphthyl group,
When group B is a substituted phenyl group, hydroxy group; sulfo group; carboxy group; C1-C4 alkyl group; C1-C4 alkoxy group; amino group; mono- or di-C1-C4 alkylamino group; acetylamino group; A benzoylamino group in which the ring is optionally substituted by a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group;
When group B is a substituted naphthyl group, from the group consisting of a hydroxy group; a sulfo group; a C1-C4 alkoxy group; and a phenylsulfonyloxy group in which the benzene ring may be substituted with a methyl group, a nitro group, or a chlorine atom; With selected substituents. ) In claim 1,
The ink set, wherein the first metal ion is at least one of sodium ion and lithium ion. In claim 1 or claim 2,
The ink set, wherein the second metal ion is at least one of potassium ion and sodium ion. In any one of Claims 1 thru | or 3,
In the general formula (1), R ¹ is a carboxy group or an unsubstituted C1-C4 alkyl group, the R ² is a sulfo C1-C4 alkoxy group, and the R ³ is a hydrogen atom, a methyl group, or an ethyl group. , Ink set. In any one of Claims 1 thru | or 4,
The group A is a substituted heterocyclic group represented by the general formula (3),
In the general formula (3), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, chlorine atom, carboxy group, sulfo group, nitro group, C1-C4 alkyl group, C1-C4 alkoxy group. An ink set which is a C1-C4 alkylsulfonyl group. In any one of Claims 1 thru | or 5,
The ink set is an ink set, wherein the dye is a compound represented by the following formula (4) or a salt thereof.

An ink set comprising the first ink and the second ink according to any one of claims 1 to 6,
A nozzle surface having nozzle holes for discharging the first ink and the second ink;
A wipe member for wiping the nozzle surface;
A droplet discharge device.

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