阅读说明：本技术 油墨组 (Ink set ) 是由 有贺友洋 滨晋太郎 隈本圣观 于 2020-01-23 设计创作，主要内容包括：本申请提供油墨组,其颜色再现性良好并且不易发生堵塞。一种油墨组,其具有：包含由式(y-1)表示的化合物或其盐的第一油墨；包含由式(m-1)表示的化合物或其盐、由式(m-2)表示的化合物或其盐、由式(m-3)表示的化合物或其盐和由式(m-4)表示的化合物或其盐中的一种或两种以上的第二油墨；以及包含由式(c-1)表示的化合物或其盐、由式(c-2)表示的化合物或其盐、由式(c-3)表示的化合物或其盐、由式(c-4)表示的化合物或其盐和由式(c-5)表示的化合物或其盐中的一种或两种以上的第三油墨。[化学式1]<Image he="308" wi="700" file="DDA0002378736770000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present application provides an ink set which is good in color reproducibility and is less likely to cause clogging. An ink set, having: a first ink containing a compound represented by the formula (y-1) or a salt thereof; a second ink containing one or two or more of a compound represented by the formula (m-1) or a salt thereof, a compound represented by the formula (m-2) or a salt thereof, a compound represented by the formula (m-3) or a salt thereof, and a compound represented by the formula (m-4) or a salt thereof; and a third ink containing one or two or more of a compound represented by the formula (c-1) or a salt thereof, a compound represented by the formula (c-2) or a salt thereof, a compound represented by the formula (c-3) or a salt thereof, a compound represented by the formula (c-4) or a salt thereof, and a compound represented by the formula (c-5) or a salt thereof. [ chemical formula1])

1. An ink set, having:

a first ink containing a compound represented by the following formula (y-1) or a salt thereof;

a second ink containing one or more of a compound represented by the following formula (m-1) or a salt thereof, a compound represented by the following formula (m-2) or a salt thereof, a compound represented by the following formula (m-3) or a salt thereof, and a compound represented by the following formula (m-4) or a salt thereof; and

a third ink containing one or more of a compound represented by the following formula (c-1) or a salt thereof, a compound represented by the following formula (c-2) or a salt thereof, a compound represented by the following formula (c-3) or a salt thereof, a compound represented by the following formula (c-4) or a salt thereof, and a compound represented by the following formula (c-5) or a salt thereof,

in the formula (m-3), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group; r³And R⁸Each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group, and the alkyl group, the alkoxy group or the aryloxy group may have at least one substituent selected from the group of substituents consisting of an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkoxy group, a cyano group, a halogen atom and an ionic group; r²、R⁴、R⁷And R⁹Each independently represents a hydrogen atom or an acylamino group represented by the following formula (m-3'), R²、R⁴、R⁷And R⁹At least one ofAn acylamino group represented by the following formula (m-3'); z represents SO₃H radical, SO₃An M group or an aminosulfonyl group, wherein M represents an ammonium ion or an alkali metal ion; r²、R³、R⁴、R⁷、R⁸And R⁹N represents an integer from 0 to 3 in the case of substitution with an ionic group, n represents an integer from 1 to 3 in the case of non-substitution with an ionic group, and is substituted in the position of at least one hydrogen atom of the aromatic ring in the presence of Z;

in the formula (m-3'), R¹¹Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or a heterocyclic group, and the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group and the heterocyclic group may have at least one substituent selected from the group of substituents consisting of an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, a cyano group, an alkylamino group, a sulfoalkyl group, a carbamoyl group, a sulfamoyl group, a sulfonamido group, a halogen atom and an ionic group; represents a bonding site to the aromatic ring of formula (m-3);

in the formula (c-1), b and c represent integers in which b is 0. ltoreq. b.ltoreq.4, c is 0. ltoreq. c.ltoreq.4, and b + c is 1. ltoreq. b + c.ltoreq.4, and the ring A¹、A²And A³Each selected from a benzene ring, a 2, 3-pyridine ring and a 3, 2-pyridine ring, and ring A¹、A²And A³At least one of which is a 2, 3-pyridine ring or a 3, 2-pyridine ring, ring A¹、A²And A³May be the same or different;

in the formula (c-4), rings A, B, C and D are each independently a six-membered ring having aromaticity, and at least one of rings A, B, C and D is a pyridine ring or a pyrazine ring; e is an alkylene group; x is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, and the substituted anilino group may further have 1 to 4 substituents selected from the group consisting of a sulfonic group, a carboxyl group, a phosphono group, an aminosulfonyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acetylamino group, a ureido group, an alkyl group, a nitro group, a cyano group, a halogen group, an alkylsulfonyl group, and an alkylthio group; y is hydroxyl or amino; a is more than or equal to 0.0 and less than or equal to 2.0, b is more than or equal to 0.0 and less than or equal to 3.0, c is more than or equal to 0.1 and less than or equal to 3.0, and a, b and c are more than or equal to 1.0 and less than or equal to a + b + c and less than or equal to 4.0;

2. the ink set according to claim 1, wherein,

the first ink further contains a compound represented by the following formula (y-2) or a salt thereof,

3. the ink set according to claim 1 or claim 2, wherein,

the second ink includes a compound represented by formula (m-2) or a salt thereof.

4. The ink set according to claim 1, wherein,

the third ink contains a compound represented by formula (c-2) or a salt thereof and a compound represented by formula (c-3) or a salt thereof.

Technical Field

The present invention relates to an ink set.

Background

Various ink sets are used for recording images by the ink jet method. The inks contained in the ink set each contain various components, and for obtaining an image of a desired color, a colorant such as a dye or a pigment is contained.

The ink used in the ink set requires properties suitable for the use and environment. For example, it is required that the ink is less susceptible to damage caused by ozone existing in the environment, moisture in the environment, or the like, and that discoloration or fading of an image recorded with the ink does not occur.

Such discoloration or fading of an image often arises from a colorant contained in an ink, and therefore, the colorant contained in the ink is improved. For example, patent document 1 proposes the following technique: an image excellent in color reproducibility, moisture resistance and gas resistance and excellent in color balance is recorded by using a yellow ink containing a specific dye.

The ink used for ink jetting forms a meniscus in the nozzle of the inkjet head. Therefore, in both the use and the stop of the ink jet apparatus, the water contained in the ink may evaporate in the vicinity of the nozzle tip. The yellow dye described in patent document 1 has high hydrophilicity, and the solubility of the dye in the ink is sensitive to a change in the water content of the ink. Therefore, there is a problem that clogging of the inkjet head is likely to occur. Therefore, an ink set which is excellent in color reproducibility and is less likely to cause clogging is required.

Patent document 1: japanese patent laid-open publication No. 2013-112729

Disclosure of Invention

In one embodiment of the ink set according to the present invention, the ink set includes:

a first ink containing a compound represented by the following formula (y-1) or a salt thereof,

[ chemical formula 1]

A second ink containing one or more of a compound represented by the following formula (m-1) or a salt thereof, a compound represented by the following formula (m-2) or a salt thereof, a compound represented by the following formula (m-3) or a salt thereof, and a compound represented by the following formula (m-4) or a salt thereof, and

[ chemical formula 2]

[ chemical formula 3]

[ chemical formula 4]

(in the formula (m-3), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group. R³And R⁸Each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group, and the alkyl group, the alkoxy group or the aryloxy group may have at least one substituent selected from the group of substituents consisting of an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkoxy group, a cyano group, a halogen atom and an ionic group. R²、R⁴、R⁷And R⁹Each independently represents a hydrogen atom or an acylamino group represented by the following formula (m-3'), R²、R⁴、R⁷And R⁹At least one of which is an acylamino group represented by the following formula (m-3'). Z represents SO₃H radical, SO₃M group (M represents ammonium ion or alkali metal ion) or aminosulfonyl. R²、R³、R⁴、R⁷、R⁸And R⁹In the case of substitution with an ionic group, n represents an integer of 0 to 3, in the case of non-substitution with an ionic group, n represents an integer of 1 to 3, and in the presence of Z, is substituted in the position of at least one hydrogen atom of the aromatic ring. )

[ chemical formula 5]

(in the formula (m-3'), R¹¹Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or a heterocyclic group, and the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group and the heterocyclic group may have a structure selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, a cyano group, an alkylamino group, a sulfo groupAt least one substituent group selected from the group consisting of an alkyl group, a carbamoyl group, an aminosulfonyl group, a sulfonamido group, a halogen atom and an ionic group. Represents a bonding site to the aromatic ring of formula (m-3). )

[ chemical formula 6]

And a third ink containing one or more of a compound represented by the following formula (c-1) or a salt thereof, a compound represented by the following formula (c-2) or a salt thereof, a compound represented by the following formula (c-3) or a salt thereof, a compound represented by the following formula (c-4) or a salt thereof, and a compound represented by the following formula (c-5) or a salt thereof.

[ chemical formula 7]

(in the formula (c-1), b and c represent integers in which b is 0. ltoreq. b.ltoreq.4, c is 0. ltoreq. c.ltoreq.4, and b + c is 1. ltoreq. b + c.ltoreq.4, and the ring A¹、A²And A³Each selected from a benzene ring, a 2, 3-pyridine ring and a 3, 2-pyridine ring, and ring A¹、A²And A³At least one of which is a 2, 3-pyridine ring or a 3, 2-pyridine ring, ring A¹、A²And A³May be the same or different. )

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

(in the formula (c-4), rings A, B, C and D are each independently a six-membered ring having aromaticity, and at least one of rings A, B, C and D is a pyridine ring or a pyrazine ring. E is an alkylene group. X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, which may further have 1 to 4 substituents selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphono group, an aminosulfonyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acetylamino group, a ureido group, an alkyl group, a nitro group, a cyano group, a halogen, an alkylsulfonyl group, and an alkylthio group. Y is a hydroxyl group or an amino group. a satisfies 0.0. ltoreq. a.ltoreq.2.0, b satisfies 0. ltoreq. b.ltoreq.3.0, c satisfies 0.1.1. ltoreq. c.ltoreq. a + b. ltoreq. 4.

[ chemical formula 11]

In the mode of the ink set described above,

the first ink may further contain a compound represented by the following formula (y-2) or a salt thereof.

[ chemical formula 12]

In any of the above-described embodiments of the ink set,

the second ink may contain a compound represented by formula (m-2) or a salt thereof.

In any of the above-described embodiments of the ink set,

the third ink may contain a compound represented by formula (c-2) or a salt thereof and a compound represented by formula (c-3) or a salt thereof.

Detailed Description

Embodiments of the present invention will be described below. The embodiments described below are examples of the present invention. The present invention is not limited to the following embodiments, and various modifications may be made without departing from the spirit of the present invention. All the configurations described below are not necessarily essential to the present invention.

1. Ink set

The ink set of the present embodiment includes a first ink, a second ink, and a third ink. The ink set may have other inks.

1.1. First ink

The ink set of the present embodiment includes the first ink. The first ink included in the ink set is included in the ink set as, for example, a yellow dye ink.

The first ink contains a compound represented by the following formula (y-1) or a salt thereof.

[ chemical formula 13]

In the formula (y-1), 4 sulfonic acid groups are contained, but the 4 sulfonic acid groups may each independently be in the form of a sulfonate. Examples of the counter ion of the salt of the compound represented by the formula (y-1) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 4 sulfonic acid groups may be the same or different. The compound represented by the formula (y-1) or a salt thereof is a yellow dye. Hereinafter, "the compound represented by the formula (y-1) or a salt thereof" may be simply referred to as "(y-1) dye".

The inventors have made various studies on a yellow dye ink and as a result, have found that an ink using the (y-1) dye is less likely to cause clogging of a nozzle of an ink jet head. The detailed mechanism of such a phenomenon is not clear, but the inventors presume that the hydrophobicity of the triazine ring-bonded 3-methyl-4-hydroxy-amino group of the (y-1) dye exerts an influence.

Further, the (y-1) dye showed better color development than other yellow dyes. Therefore, by including the first ink in the ink set of the present embodiment, the color reproduction range represented by the Gamut volume or the like can be expanded.

1.2.2. Other dyes

The first ink may further contain a compound represented by the following formula (y-2) or a salt thereof in addition to the dye (y-1).

[ chemical formula 14]

In the formula (y-2), 4 carboxyl groups are contained, but each of the 4 carboxyl groups independently may be in the form of a carboxylate. Examples of the counter ion of the salt of the compound represented by the formula (y-2) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 4 carboxyl groups may be the same or different. The compound represented by the formula (y-2) or a salt thereof is a yellow dye. Hereinafter, "the compound represented by the formula (y-2) or a salt thereof" may be simply referred to as "(y-2) dye".

The first ink may further contain a dye represented by the following formula (y-3) in addition to the dye (y-1).

[ chemical formula 15]

In the formula (y-3), 4 carboxyl groups are contained, but each of the 4 carboxyl groups independently may be in the form of a carboxylate. Examples of the counter ion of the salt of the compound represented by the formula (y-3) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 4 carboxyl groups may be the same or different. The compound represented by the formula (y-3) or a salt thereof is a yellow dye. Hereinafter, "the compound represented by the formula (y-3) or a salt thereof" may be simply referred to as "(y-3) dye".

The first ink may contain one or two or more dyes selected from the group consisting of (y-2) dyes and (y-3) dyes. In this case, however, the content of the (y-1) dye in the first ink is preferably 40.0% by mass or more and 99.0% by mass or less, more preferably 50.0% by mass or more and 90.0% by mass or less, and still more preferably 60.0% by mass or more and 90.0% by mass or less, with respect to the total amount of the dye contained in the first ink.

The above dye (y-1) exhibited a yellow color, but slightly reddish. On the other hand, the dyes (y-2) and (y-3) are yellow and slightly greenish. Therefore, by including these dyes in the first ink, the color expression range of the ink set can be further expanded.

The first ink may contain another yellow dye, but the effect of widening the color expression range is considered to be small. When the first ink contains another yellow dye, the content of the (y-1) dye in the first ink is preferably 40.0 mass% or more and 99.0 mass% or less with respect to the total amount of the dye contained in the first ink.

1.1.2. Other ingredients

The first ink of the present embodiment may contain a surfactant, an organic solvent, water, and other components.

(1) Surface active agent

The first ink may contain a surfactant. The surfactant has a function of lowering the surface tension of the first ink and improving wettability with a recording medium or a substrate. Among the surfactants, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used.

The acetylene glycol surfactants are not particularly limited, and include, for example, Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all of which are trade names, manufactured by Air Products & Chemicals), O L FINE 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 of which are trade names, manufactured by Acety L, ENO 48363, E P, E-8678, and Fine research and E-100 (all of which are trade names, manufactured by chemical industries).

The silicone surfactant is not particularly limited, and a silicone compound is preferably exemplified, and examples of the silicone compound include polyether-modified organosiloxanes, and commercial products of the polyether-modified organosiloxanes include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (trade names, manufactured by Nippon chemical Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (trade names, manufactured by shin-Shih chemical industries, Ltd.).

As the fluorine-based surfactant, a fluorine-modified polymer is preferably used, and specific examples thereof include BYK-3440 (manufactured by Nippon chemical Co., Ltd.), SURF L ON S-241, S-242, S-243 (hereinafter, referred to as a trade name, manufactured by AGC SEIMI CHEMICA L Co., Ltd.), Ftergent 215M (manufactured by NEOS Co., Ltd.), and the like.

In the case where the first ink contains a surfactant, a plurality of surfactants may be contained. The content of the surfactant in the case where the first ink is contained is preferably 0.1% by mass or more and 2.0% by mass or less, more preferably 0.2% by mass or more and 1.5% by mass or less, and still more preferably 0.3% by mass or more and 1.0% by mass or less, based on the total mass.

(2) Organic solvent

The first ink may contain an organic solvent. Although the first ink may not contain an organic solvent, the first ink can easily achieve both drying property and ejection stability by containing an organic solvent. The organic solvent is preferably a water-soluble organic solvent.

One of the functions of the organic solvent is as follows: the wettability of the first ink to the recording medium is improved, and the moisture retention of the first ink is improved. As the organic solvent, there may be mentioned: esters, alkylene glycol ethers, cyclic esters, nitrogen-containing solvents, polyhydric alcohols, and the like. Examples of the nitrogen-containing solvent include cyclic amides and acyclic amides. Examples of the acyclic amides include alkoxyalkylamides.

Examples of esters include: glycol monoacetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and methoxybutyl acetate; glycol diesters such as ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, propylene glycol acetate propionate, propylene glycol acetate butyrate, dipropylene glycol acetate butyrate and dipropylene glycol acetate propionate.

The alkylene glycol ether may be a monoether or diether of an alkylene glycol, and is preferably an alkyl ether. Specific examples thereof include: alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether; and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ether ethyl ether, diethylene glycol methyl ether butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl ether butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

Examples of the cyclic ester include cyclic esters (lactones) such as β -propiolactone, γ -butyrolactone, -valerolactone, -caprolactone, β -butyrolactone, β -valerolactone, γ -valerolactone, β -caprolactone, γ -caprolactone, β -heptolactone, γ -heptolactone, γ -octolactone, -nonlactone, -nonolactone, and-decalactone, and compounds in which the hydrogen of a methylene group adjacent to a carbonyl group of the cyclic ester is substituted with an alkyl group having 1 to 4 carbon atoms.

Examples of the alkoxyalkylamides include: 3-methoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-diethylpropionamide, 3-methoxy-N, N-methylethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-diethylpropionamide, 3-ethoxy-N, N-methylethylpropionamide, 3-N-butoxy-N, N-dimethylpropionamide, 3-N-butoxy-N, N-diethylpropionamide, 3-N-butoxy-N, N-methylethylpropionamide, 3-N-propoxy-N, N-dimethylpropionamide, 3-N-propoxy-N, N-diethylpropionamide, 3-N-propoxy-N, N-methylethylpropionamide, 3-isopropoxy-N, N-dimethylpropionamide, 3-isopropoxy-N, N-diethylpropionamide, 3-isopropoxy-N, N-methylethylpropionamide, 3-tert-butoxy-N, N-dimethylpropionamide, 3-tert-butoxy-N, N-diethylpropionamide, 3-tert-butoxy-N, N-methylethylpropionamide, and the like.

Examples of the cyclic amides include lactams, for example: pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone and 1-butyl-2-pyrrolidone. These cyclic amides are preferable, and 2-pyrrolidone is particularly more preferable, from the viewpoint of promoting film formation of resin particles described later.

Further, as the acyclic amides, alkoxyalkylamides, which are compounds represented by the following formula (1), are also preferably used.

R¹-O-CH₂CH₂-(C＝O)-NR²R³……(1)

In the above formula (1), R¹Represents an alkyl group having 1 to 4 carbon atoms, R²And R³Each independently represents a methyl group or an ethyl group. The "alkyl group having 1 to 4 carbon atoms" may be a straight-chain or branched-chain alkyl group, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, or a tert-butyl group. One compound represented by the above formula (1) may be used alone, or two or more compounds may be used in combination.

As the polyhydric alcohol, there may be mentioned: 1, 2-alkanediols (e.g., ethanediol, propanediol (also known as propane-1, 2-diol), triethylene glycol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-octanediol, and other alkanediols), polyols (polyols) other than 1, 2-alkanediols (e.g., diethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol (also known as 1, 3-butylene glycol), 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-ethyl-2-methyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, etc.), 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 3-methyl-1, 3-butanediol, 2-ethyl-1, 3-hexanediol, 3-methyl-1, 5-pentanediol, 2-methylpentane-2, 4-diol, trimethylolpropane, glycerol, etc.), etc.

In the first ink, one kind of the organic solvent exemplified above may be used alone, or two or more kinds may be used in combination. When the organic solvent is added to the first ink, the total content of the organic solvent with respect to the entire first ink is 3.0 mass% or more and 30.0 mass% or less, preferably 5.0 mass% or more and 25.0 mass% or less, and more preferably 10.0 mass% or more and 20.0 mass% or less.

(3) Water (W)

The first ink may contain water. The first ink is preferably aqueous. Aqueous refers to compositions containing water as one of the major solvent components. Water may be contained as a main solvent component, and water is a component that evaporates and scatters by drying. The water is preferably pure water or ultrapure water from which ionic impurities have been removed as much as possible, such as ion-exchanged water, ultrafiltration water, reverse osmosis water, and distilled water. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be suppressed when the first ink is stored for a long period of time, and therefore, it is preferable. The content of water is preferably 75.0% by mass or more, more preferably 80.0% by mass or more and 98% by mass or less, and further preferably 85.0% by mass or more and 95.0% by mass or less, with respect to the total amount of the first ink.

(4) Others

The first ink may contain, as other components, a pH adjuster, a mildewcide/antiseptic agent, a chelating agent, a rust inhibitor, a mildewcide, an antioxidant, an antireductant, an evaporation accelerator, and the like.

Examples of the pH adjuster include: and aminoalcohols such as ureas, amines, morpholines, piperazines, and triethanolamine. As ureas, there may be mentioned: urea, ethylene urea, tetramethylurea, thiourea, 1, 3-dimethyl-2-imidazolidinone, and the like, and betaines (trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, N-trimethylalanine, N-triethylalanine, N-triisopropylalanine, N-trimethylmethylalanine, carnitine, acetyl carnitine, and the like), and the like. Examples of the amines include diethanolamine, triethanolamine, and triisopropanolamine. By containing the pH adjuster, for example, elution of impurities from a member forming the ink flow path can be suppressed or promoted, and the washability of the first ink can be adjusted.

Examples of the antifungal agent/preservative include Proxel CR L, Proxel BDN, Proxel GX L, Proxel X L2, Proxel IB, and Proxel TN (all trade names, manufactured by L onza corporation).

Examples of the chelating agent include: ethylenediaminetetraacetate (EDTA), nitrilotriacetate of ethylenediamine, hexametaphosphate, pyrophosphate, metaphosphate, and the like.

1.2. Second ink

The ink set of the present embodiment includes the second ink. The second ink included in the ink set is included in the ink set as, for example, a magenta dye ink. The second ink contains a magenta-based dye.

1.2.1. Magenta dye

The second ink of the present embodiment contains, as a magenta dye, one or more selected from the group consisting of a compound represented by the following formula (m-1) or a salt thereof, a compound represented by the following formula (m-2) or a salt thereof, a compound represented by the following formula (m-3) or a salt thereof, and a compound represented by the following formula (m-4) or a salt thereof.

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

(in the formula (m-3), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group. R³And R⁸Each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group, and the alkyl group, the alkoxy group or the aryloxy group may be at least one substituent selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, hydroxyl groups, carbamoyl groups, aminosulfonyl groups, alkoxy groups, cyano groups, halogen atoms and ionic groups. R²、R⁴、R⁷And R⁹Each independently represents a hydrogen atom or an acylamino group represented by the following formula (m-3'), R²、R⁴、R⁷And R⁹At least one of which is an acylamino group represented by the following formula (m-3'). Z represents SO₃H radical, SO₃M group (M represents ammonium ion or alkali metal ion) or aminosulfonyl. R²、R³、R⁴、R⁷、R⁸And R⁹In the case of substitution with an ionic group, n represents an integer of 0 to 3, in the case of non-substitution with an ionic group, n represents an integer of 1 to 3, and in the presence of Z, is substituted in the position of at least one hydrogen atom of the aromatic ring. )

[ chemical formula 19]

(in the formula (m-3'), R¹¹Represents alkyl, cycloalkyl, aryl, aralkyl, alkenyl orThe heterocyclic group, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group and the heterocyclic group may have at least one substituent selected from the group of substituents consisting of an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, a cyano group, an alkylamino group, a sulfoalkyl group, a carbamoyl group, a sulfamoyl group, a sulfonamido group, a halogen atom and an ionic group. Represents a bonding site to the aromatic ring of formula (m-3). )

[ chemical formula 20]

Examples of the counter ion of the salt of the compound represented by the formula (m-1) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 4 carboxyl groups and 2 sulfonic acid groups may be the same or different. The compound represented by the formula (m-1) or a salt thereof is a magenta-based dye. Hereinafter, the "compound represented by the formula (m-1) or a salt thereof" may be simply referred to as "dye (m-1)".

Examples of the counter ion of the salt of the compound represented by the formula (m-2) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 4 carboxyl groups and 6 sulfonic acid groups may be the same or different. The compound represented by the formula (m-2) or a salt thereof is a magenta-based dye. Hereinafter, the "compound represented by the formula (m-2) or a salt thereof" may be simply referred to as "dye (m-2)".

Examples of the counter ion of the salt of the compound represented by the formula (m-3) include a hydrogen ion (proton), lithium, sodium, potassium, and ammonium. The compound represented by the formula (m-3) or a salt thereof is a magenta-based dye. Hereinafter, the "compound represented by the formula (m-3) or a salt thereof" may be simply referred to as "dye (m-3)".

Examples of the counter ion of the salt of the compound represented by the formula (m-4) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 4 sulfonic acid groups may be the same or different. The compound represented by the formula (m-4) or a salt thereof is a magenta-based dye. Hereinafter, the "compound represented by the formula (m-4) or a salt thereof" may be simply referred to as "dye (m-4)".

The second ink may contain other magenta-based dyes. Other magenta dyes include: c.i. direct red 1,4, 9, 80, 81, 225, c.i. acid red 52, 80, 82, 227, 249, 254, 289, etc.

In the case where another magenta dye is contained in the second ink, the total content of the (m-1) to (m-4) dyes in the second ink is preferably 40.0 mass% or more and 99.0 mass% or less with respect to the total amount of the dyes contained in the second ink, from the viewpoint of a wide color expression range.

1.2.2. Other ingredients

The second ink of the present embodiment may contain a surfactant, an organic solvent, water, and other components. These components are the same as those described in the first ink, and thus the description thereof is omitted.

1.3. Third ink

The ink set of the present embodiment includes the third ink. The third ink included in the ink set is included in the ink set as, for example, a cyan dye ink. The third ink contains a cyan dye.

1.2.1. Cyan dye

The third ink of the present embodiment contains, as a cyan dye, one or more selected from the group consisting of a compound represented by the following formula (c-1) or a salt thereof, a compound represented by the following formula (c-2) or a salt thereof, a compound represented by the following formula (c-3) or a salt thereof, a compound represented by the following formula (c-4) or a salt thereof, and a compound represented by the following formula (c-5) or a salt thereof.

[ chemical formula 21]

(in the formula (c-1), b and c represent integers in which b is 0. ltoreq. b.ltoreq.4, c is 0. ltoreq. c.ltoreq.4, and b + c is 1. ltoreq. b + c.ltoreq.4, and the ring A¹、A²And A³Each selected from a benzene ring, a 2, 3-pyridine ring and a 3, 2-pyridine ring, and ring A¹、A²And A³At least one of which is a 2, 3-pyridine ring or a 3, 2-pyridine ring, ring A¹、A²And A³May or may not be the sameThe same is true. )

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

(in the formula (c-4), rings A, B, C and D are each independently a six-membered ring having aromaticity, and at least one of rings A, B, C and D is a pyridine ring or a pyrazine ring. E is an alkylene group. X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, which may further have 1 to 4 substituents selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphono group, an aminosulfonyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acetylamino group, a ureido group, an alkyl group, a nitro group, a cyano group, a halogen, an alkylsulfonyl group, and an alkylthio group. Y is a hydroxyl group or an amino group. a satisfies 0.0. ltoreq. a.ltoreq.2.0, b satisfies 0. ltoreq. b.ltoreq.3.0, c satisfies 0.1.1. ltoreq. c.ltoreq. a + b. ltoreq. 4.

[ chemical formula 25]

Examples of the counter ion of the salt of the compound represented by the formula (c-1) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ion of the sulfonic acid group may be the same or different. The compound represented by the formula (c-1) or a salt thereof is a cyan dye. Hereinafter, "the compound represented by the formula (c-1) or a salt thereof" may be simply referred to as "(c-1) dye".

Examples of the counter ion of the salt of the compound represented by the formula (c-2) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 4 sulfonic acid groups may be the same or different. The compound represented by the formula (c-2) or a salt thereof is a cyan-based dye. Hereinafter, "the compound represented by the formula (c-2) or a salt thereof" may be simply referred to as "(c-2) dye".

Examples of the counter ion of the salt of the compound represented by the formula (c-3) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 2 sulfonic acid groups may be the same or different. The compound represented by the formula (c-3) or a salt thereof is a cyan-based dye. Hereinafter, "the compound represented by the formula (c-3) or a salt thereof" may be simply referred to as "(c-3) dye".

Examples of the counter ion of the salt of the compound represented by the formula (c-4) include a hydrogen ion (proton), lithium, sodium, potassium, and ammonium. The compound represented by the formula (c-4) or a salt thereof is a cyan-based dye. Hereinafter, the "compound represented by the formula (c-4) or a salt thereof" may be simply referred to as "dye (c-4)".

Examples of the counter ion of the salt of the compound represented by the formula (c-5) include a hydrogen ion (proton), lithium, sodium, potassium, ammonium, and the like, and the counter ions of 3 sulfonic acid groups may be the same or different. The compound represented by the formula (c-5) or a salt thereof is a cyan-based dye. Hereinafter, the "compound represented by the formula (c-5) or a salt thereof" may be simply referred to as "dye (c-5)".

The third ink may contain other cyan-based dyes. Examples of other cyan dyes include: c.i. direct blue 1,2, 15, 71, 86, 87, 98, 165, 199, 202, etc.

In the case where another cyan dye is contained in the third ink, the total content of the dyes (c-1) to (c-5) in the third ink is preferably 40.0 mass% to 99.0 mass% based on the total amount of the dyes contained in the third ink, from the viewpoint of a wide color expression range.

1.2.2. Other ingredients

The third ink of the present embodiment may contain a surfactant, an organic solvent, water, and other components. These components are the same as those described in the first ink, and thus the description thereof is omitted.

1.3. Physical properties of the ink

The first ink, the second ink, and the third ink are preferably attached to a recording medium such as paper, film, cloth, or the like by an inkjet method. Therefore, the viscosity of each ink at 20 ℃ is preferably 1.5 to 15.0 mPas, more preferably 1.5 to 5.0 mPas, and still more preferably 1.5 to 3.6 mPas. When each ink is attached to a recording medium by an ink jet method, a predetermined image can be formed easily and efficiently.

From the viewpoint of optimizing the wet spreading properties on the recording medium, the surface tensions of the first ink, the second ink, and the third ink at 25.0 ℃ are preferably 40.0mN/m or less, preferably 38.0mN/m or less, more preferably 35.0mN/m or less, and still more preferably 30.0mN/m or less. The surface tension can be measured by confirming the surface tension when the platinum plate is wetted with the composition in an environment of 25.0 ℃ by using an automatic surface tensiometer CBVP-Z (manufactured by synghoni interface science).

2. Examples and comparative examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Hereinafter, "part(s)" and "%" are based on mass unless otherwise specified.

2.1. Preparation of dye inks

Yellow dye inks Y1 to Y15 having different material compositions were prepared in accordance with the material compositions shown in table 1, magenta dye inks M1 to M9 having different material compositions were prepared in accordance with the material compositions shown in table 2, and cyan dye inks C1 to C9 having different material compositions were prepared in accordance with the material compositions shown in table 3. Each ink was prepared by: the materials shown in tables 1 to 3 were put into a vessel, stirred and mixed for 2 hours by a magnetic stirrer, and then filtered by a membrane filter having a pore size of 5 μm to remove impurities such as wastes and coarse particles. All the numerical values in tables 1 to 4 represent mass%, and pure water was added so that the total mass of the ink became 100 mass%.

TABLE 1

TABLE 2

TABLE 3

The main materials in tables 1 to 3 are as follows.

(y-1) to (y-3): sodium salts of the dyes (y-1) to (y-3) are used.

(y-4): a compound represented by the following formula (y-4) is used.

[ chemical formula 26]

(y-5): a compound represented by the following formula (y-5) is used.

[ chemical formula 27]

(m-1) to (m-3): the dyes (m-1) to (m-3) were the same, and for (m-1), a sodium salt was used, for (m-2), a sodium salt and an ammonium salt were used, and for (m-3), a sodium salt was used.

Further, with respect to (m-3), the following is satisfied:

(in the formula (m-3), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group. R³And R⁸Each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group, and the alkyl group, the alkoxy group or the aryloxy group may have a structure selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an alkoxy group, a cyano group, a hydroxyl group, a carbamoyl group,At least one substituent group of a substituent group consisting of a halogen atom and an ionic group. R²、R⁴、R⁷And R⁹Each independently represents a hydrogen atom or an acylamino group represented by the formula (m-3'), R²、R⁴、R⁷And R⁹At least one of (a) is an acylamino group represented by the formula (m-3'). Z represents SO₃H radical, SO₃M group (M represents ammonium ion or alkali metal ion) or aminosulfonyl. R²、R³、R⁴、R⁷、R⁸And R⁹In the case of substitution with an ionic group, n represents an integer of 0 to 3, in the case of non-substitution with an ionic group, n represents an integer of 1 to 3, and in the presence of Z, is substituted in the position of at least one hydrogen atom of the aromatic ring. )

(in the formula (m-3'), R¹¹Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or a heterocyclic group, and the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group and the heterocyclic group may have at least one substituent selected from the group of substituents consisting of an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, a cyano group, an alkylamino group, a sulfoalkyl group, a carbamoyl group, a sulfamoyl group, a sulfonamido group, a halogen atom and an ionic group. Represents a bonding site to the aromatic ring of formula (m-3). )

As (m-4), a lithium salt of the above-mentioned (m-4) dye was used.

As (m-5), a compound represented by the following formula (m-5) was used.

[ chemical formula 28]

With respect to (m-5), the following is satisfied:

(in the formula (m-5), n₁Is 1 or 2, three M are respectively sodium or ammonium, the three M can be the same or different, R⁰Is a C1-8 monoalkylamino group substituted with a carboxyl group. )

(c-1) to (c-5): the dyes (c-1) to (c-5) are the above dyes, and sodium salts are used for (c-1) to (c-3).

As (c-6), a compound represented by the following formula (c-6) was used.

[ chemical formula 29]

With respect to (c-6), the following is satisfied:

(in the formula (c-6), ring A¹、A²And A³Each selected from a benzene ring, a 2, 3-pyridine ring and a 3, 2-pyridine ring, and ring A¹、A²And A³At least one of which is a 2, 3-pyridine ring or a 3, 2-pyridine ring, ring A¹、A²And A³A is equal to or different from 1.0 and less than or equal to 3.0, b is equal to or less than 0.2 and less than or equal to 1.8, c is equal to or less than 0.8 and less than or equal to 1.6, a, b and c are equal to or less than 0 and less than or equal to a + b + c and less than or equal to 4, x is an integer equal to or less than 1 and less than or equal to z and less than or equal to 3, R¹Is a linear alkylene group having 1 to 6 carbon atoms. )

Surfynol 104PG 50: (trade name, manufactured by Air Products & Chemicals Co.): acetylenediol surfactants

O L FINE E1010 (trade name, manufactured by Nissan chemical industries, Ltd.) acetylene glycol surfactant

Proxel X L2 (trade name, manufactured by L onza corporation) mildewcide/antiseptic

EDTA: disodium ethylenediaminetetraacetic acid (reagent): chelating agents

2.2. Evaluation method

2.2.1. Evaluation of color development Properties (color reproduction Range (Gamut)) of the respective ink sets

The ink sets of the examples shown in Table 4 were filled in an ink jet printer (trade name "EW-M660 FT", manufactured by Seiko Epson corporation), single color/secondary color patches were printed on plain paper (Xerox 4200: trade name, manufactured by Fuji Schuler Co., Ltd.), OD values and L ab were measured, and Gamut volumes were calculated.A printing environment was set to 25 ℃ and 40% RH., and the evaluation results were shown in Table 4, according to the following evaluation criteria.

A: gamut volume value of 160000 or more

B: a Gamut volume value of 155000 or more and less than 160000

C: gamut volume value of 150000 or more and less than 155000

D: gamut volume value less than 150000

2.2.5. Evaluation of clogging recovery (clogging resistance) of each ink set

The ink sets shown in tables 1 to 3 were filled in an ink jet printer (trade name "EW-M660 FT", manufactured by seiko eprunox corporation), and the power supply was turned off during printing, and the environmental setting was performed without covering the ink jet head. After leaving in an atmosphere of 40 ℃ and 40% RH for one week, the number of cleanings required until normal ejection was counted. The evaluation was performed according to the following criteria, and the results are shown in table 4.

A: 1 time of

B: 2 times (one time)

C: 3 times of

D: 4 times (twice)

TABLE 4

2.3. Evaluation results

As shown in Table 4, the ink set of each example having a yellow ink (first ink) containing a (y-1) dye, a magenta ink (second ink) containing one or two or more of (m-1) dye, (m-2) dye, (m-3) dye and (m-4) dye, and a cyan ink (third ink) containing one or two or more of (c-1) dye, (c-2) dye, (c-3) dye, (c-4) dye and (c-5) dye was high in color development (Gamut volume) and good in clogging recovery.

The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configurations (for example, configurations having the same functions, methods, and results, or configurations having the same objects and effects) as those described in the embodiments. The present invention includes a configuration in which the nonessential portions of the configurations described in the embodiments are replaced. The present invention includes a configuration that can achieve the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. The present invention includes a configuration obtained by adding a known technique to the configuration described in the embodiment.