JP7283655B2 - Water-based dye dispersion for water-based ink and water-based ink - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-based dye dispersion for water-based inks and water-based inks, and more particularly to a water-based dye dispersion used for manufacturing water-based inks for inkjet printing and water-based inks containing the same. It is something to do.

Inkjet printing is widely used in copiers, printers, and facsimiles for home and office use. , ceramic products such as tiles, resin products such as films, and textile products such as fabrics. In such various printing, various dyes are used according to the type of coloring base material. For example, water-insoluble dyes such as disperse dyes are used for printing on textile products such as fabrics made of hydrophobic fibers. As a method of printing on a fabric made of hydrophobic fibers using such a water-insoluble dye, there is a printing method (direct printing method) in which the dye is dyed by heat treatment such as steaming after the ink is directly applied to the fiber. , After ink is applied to an intermediate recording medium such as paper, the fibers are brought into contact with the intermediate recording medium, and the dye is sublimated and transferred from the intermediate recording medium to the fibers by heat. , see Patent Document 1).

Since water is generally used as a solvent in inks used in printing methods using such water-insoluble dyes, it is necessary to disperse the water-insoluble dyes in water. Therefore, dye derivatives are generally used as dispersants and dispersion aids. However, there are cases where the particles containing the water-insoluble dye in the ink aggregate and sediment during or after preparation, and the dispersion stability during preparation and storage is not always sufficient. In addition, if the stability during storage is not sufficient, the stability during ejection is also insufficient, for example, in an inkjet printing apparatus.

JP 2015-93957 A

As described above, in inks in which water-insoluble dyes such as disperse dyes are dispersed in water, even if conventional dispersants are used, particles in the ink may aggregate and the dispersion stability during storage may not be sufficient. Further, as a result of studies by the present inventors, it has been found that even if a dispersant and a dye derivative are used, even if the dispersion stability is maintained, the printed matter may be It has been found that the color may differ. In particular, when the direct textile printing method is adopted, it has been found that the color tone of the printed matter may differ.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a water-based dye dispersion for a water-based ink and a water-based ink which have good dispersion stability and can form a printed matter of desired color regardless of the textile printing method.

The inventor of the present invention has made intensive studies to solve the problems described above. As a result, by using a specific dye derivative as a dispersing aid as a dispersing aid, it has good dispersion stability and can form a printed matter of desired color regardless of the printing method. It has been found that ink can be provided.

A first aspect of the present invention relates to a water-based dye dispersion for water-based inks, comprising a dye derivative represented by the following formula (1), a water-insoluble dye, a dispersant and water.

(In formula (1), R ¹ represents an amino group, R ² represents a group represented by the following formula (2) or (3), R ³ represents a hydroxyl group or —NH—R ⁸ —NR ⁹ R ¹⁰ R ⁸ represents an alkylene group or phenylene group having 1 to 4 carbon atoms, and R ⁹ and R ¹⁰ represent independently selected alkyl groups having 1 to 4 carbon atoms. indicates a real number greater than 0 and less than or equal to 2.)

(In formula (2), * indicates a bond.)

(In Formula (3), R ⁴ to R ⁷ independently represent a hydrogen atom or a halogen atom. * represents a bond.)

In an embodiment of the present invention, the dye derivative represented by the formula (1) may be a dye derivative represented by the following formula (4). In formula (4), R ¹ , R ² and R ³ are the same as in formula (1) above.

In an embodiment of the present invention, R ¹ in formula (1) is —NH ₂ , —NHR ⁸ (wherein R ⁸ represents a hydrocarbon group having 1 to 4 carbon atoms) and —NR ⁹ R ¹⁰ (wherein R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 1 to 4 carbon atoms).

A second aspect of the present invention relates to a water-based ink containing the water-based dye dispersion for water-based ink and a surfactant. In an embodiment of the present invention, the water-based ink may be for inkjet recording.

According to the present invention, it is possible to provide a water-based dye dispersion for water-based ink and a water-based ink which have good dispersion stability and can form a printed matter of desired color regardless of the textile printing method.

Embodiments of the present invention will be described below.

(Water-based dye dispersion for water-based ink)
A water-based dye dispersion for water-based ink according to an embodiment of the present invention includes a dye derivative represented by the following formula (1), a water-insoluble dye, a dispersant, and water.

(In formula (1), R ¹ represents an amino group, R ² represents a group represented by the following formula (2) or (3), R ³ represents a hydroxyl group or —NH—R ⁸ —NR ⁹ R ¹⁰ R ⁸ represents an alkylene group or phenylene group having 1 to 4 carbon atoms, and R ⁹ and R ¹⁰ represent independently selected alkyl groups having 1 to 4 carbon atoms. indicates a real number greater than 0 and less than or equal to 2.)

(In formula (2), * indicates a bond.)

(In Formula (3), R ⁴ to R ⁷ independently represent a hydrogen atom or a halogen atom. * represents a bond.)

Thus, by including the dye derivative represented by formula (1), it is possible to stably maintain the dispersed state of the particles containing the water-insoluble dye, and even in the water-based ink containing the dye dispersion, It is possible to stably maintain the dispersed state of the particles containing the insoluble dye. In addition, it is possible to form a printed material with a desired color regardless of the textile printing method. In particular, in the direct printing method, it is possible to form a printed matter with a color similar to that in the case of using no dye derivative or in the case of the sublimation type printing method. In the sublimation-type textile printing method, a printed matter printed on an intermediate recording medium is sublimated and transferred to fibers by heat. Therefore, in the sublimation printing method, even if a dye derivative is used, it is possible to form a printed matter having the same color tone as when the dye derivative is not used, as long as the dye derivative does not sublimate. In the direct textile printing method, the dye derivative remains in the printed matter because the textile is printed directly. As a result, the color tone inherent to the dye derivative affects the color tone of the printed matter. However, by using the dye derivative represented by formula (1), the influence on the color can be reduced.

In formula (1), R ¹ may be an amino group, for example, a group selected from —NH ₂ , —NHR ⁸ and —NR ⁹ R ¹⁰ , and —NR ⁹ R ¹⁰ groups are preferred. Here, R ⁸ , R ⁹ and R ¹⁰ may be hydrocarbon groups having 1 to 4 carbon atoms. In addition, R ⁹ and R ¹⁰ may each independently be these groups. Examples of hydrocarbon groups include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and alicyclic hydrocarbon groups. Moreover, these hydrocarbon groups may have a substituent. Such substituents include amino groups, hydroxy groups, nitro groups, and the like. Among such hydrocarbon groups, aliphatic hydrocarbon groups having 1 to 3 carbon atoms are preferred, and unsubstituted aliphatic hydrocarbon groups having 1 to 3 carbon atoms are more preferred.

In the group represented by formula (3), R ⁴ to R ⁷ in the formula may be independently represented by hydrogen atoms or halogen atoms, and at least one of R ⁴ to R ⁷ is halogen Atoms are preferred. In this case, any one of R ⁴ to R ⁷ may be a halogen atom, but for example, R5 is preferably a halogen atom. A halogen atom may be a chlorine atom, a bromine atom, or the like, but a chlorine atom is preferable.

In formula (1), the bonding positions of R ¹ and R ² are not particularly limited, but those represented by the following formula (4) are preferable.

In formula (4), R ¹ to R ³ and n are the same as in formula (1).

The dye derivative represented by formula (1) can be produced according to a conventionally known method for producing a dye derivative.

From the viewpoint of dispersion stability, the content of the dye derivative in the dye dispersion is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the water-insoluble dye.

The water-insoluble dye is not particularly limited as long as it is insoluble or sparingly soluble in water. Examples of such dyes include disperse dyes, oil-soluble dyes, acid dyes, and the like. In the present invention, "water-insoluble" means that the solubility in water at 25°C is 1 g/m ³ or less.

Specific examples of disperse dyes include the following when indicated by color index (C.I.) numbers.
C. I. Disperse Yellow 3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71 , 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141 , 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, etc.;
C. I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49 , 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139 , 142, etc.;
C. I. disperse thread 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 289, 298, 302, 303, 310, 311, 312, 320, 324, 328, etc.;
C. I. Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63 , 69, 77, etc.;
C. I. Disperse Green 6:1, 9, etc.;
C. I. Disperse Brown 1, 2, 4, 9, 13, 19, etc.;
C. I. Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79 , 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143 , 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211 , 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 359, etc.;
C. I. Disperse Black 1, 3, 10, 24 and so on.

Specific examples of the oil-soluble dye include the following when indicated by a color index (C.I.) number.
C. I. Solvent Yellow 1, 2, 3, 5, 6, 13, 14, 16, 19, 21, 22, 29, 33, 36, 37, 38, 39, 40, 43, 44, 45, 47, 62, 63, 71, 76, 81, 85, 86, 93, 114, 151, 157, 163, etc.;
C. I. Solvent Orange 2, 7, 55, 60, 67, etc.;
C. I. solvent red 1, 3, 8, 18, 23, 24, 27, 35, 36, 37, 38, 39, 40, 43, 48, 49, 51, 52, 58, 60, 65, 69, 81, 86, 89, 91, 92, 97, 99, 100, 109, 111, 118, 119, 122, 125, 127, 130, 132, 135, 145, 146, 149, 150, 151, 155, 168, 176, 179, 180, 181, 195, 207, 218, 225, 233, etc.;
C. I. solvent violet 13, 31, 36, 37, 57, 59, etc.;
C. I. solvent blue 14, 24, 25, 26, 34, 35, 36, 37, 38, 39, 42, 43, 44, 45, 48, 52, 53, 55, 59, 63, 67, 70, 78, 83, 87, 94, 104, 105, 111, 132, 136, etc.;
C. I. Solvent Green 3, 5, 7, 20, 28, etc.;
C. I. solvent black 3, 5, 7, 8, 14, 17, 19, 20, 22, 24, 26, 27, 28, 43;

Water-insoluble dyes may be used alone or in combination of two or more.

The average particle diameter of the water-insoluble dye can be appropriately determined depending on the application. is preferred. Incidentally, the average particle size can be measured by a general method such as a dynamic light scattering method or a laser diffraction method.

The content (solid content) of the water-insoluble dye is preferably 1 to 25% by weight based on the total weight of the dye dispersion, from the viewpoint of ensuring freedom of composition during ink preparation and coloring power.

The dispersant is not particularly limited, and examples thereof include resin-type dispersants and surfactant-type dispersants. Further, the resin type dispersant has an amine value of 0 mg-KOH/g and an acid value of greater than 0 mg-KOH/g due to the difference between the acid value and the amine value of the resin. There are amine value type dispersants having a value of 0 mg- KOH/g and an amine value greater than 0 mg-KOH/g , and dispersants having an acid value and an amine value greater than 0 mg-KOH/g . There is also a resin-type dispersant having an acid value and an amine value of 0 mg-KOH/g .

Resin-type dispersants include, for example, polyurethane; polyester; unsaturated polyamide; phosphoric acid ester; polycarboxylic acid and its amine salt, ammonium salt, alkylamine salt; Modified polyacrylate; water-soluble polymer compounds such as alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyvinylpyrrolidone, gum arabic; styrene-acrylic acid resin, styrene-methacrylic acid resin, styrene-acrylic acid Acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid-acrylic acid ester resin, isobutylene-maleic acid resin, vinyl-ester resin, rosin-modified maleic acid resins containing ethylenic double bonds such as acid resins; amine resins such as polyallylamine, polyvinylamine and polyethyleneimine; and the like.

Various resin-type dispersants are commercially available, and specific examples thereof are as follows, but are not limited to these.
Nippon Lubrizol Co., Ltd.: Solsperse 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 38500, 39000, 55000, 41000,
BYK-Chemie Japan Co., Ltd.: Disperbyk 108, 110, 112, 140, 142, 145, 161, 162, 163, 164, 166, 167, 171, 174, 182, 190, 2000, 2001, 2015, 2050, 2070, 2150, LPN6919, LPN21116,
BASF Corporation: EFKA 4401, 4403, 4406, 4330, 4340, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 5064, 5207, 5244, PX4701,
Ajinomoto Fine-Techno Co., Inc.: Ajisper-PB821 (F), PB822, PB880,
Kawaken Fine Chemicals Co., Ltd.: Hinoact T-8000,
Kusumoto Kasei Co., Ltd.: Disparon PW-36, Disparon DA-325, 375, 7301, etc.

The molecular weight of the resin-type dispersant is not particularly limited, but a weight average molecular weight of 1,000 to 30,000 is preferable.

The acid value and amine value of the resin-type dispersant are determined by the functional groups contained in the resin constituting the resin-type dispersant and their content. The acid value (acid value when converted to solid content) can be determined, for example, by a method based on DIN EN ISO 2114, and the amine value (amine value when converted to solid content) can be determined, for example, from DIN 16945. It can be obtained by a method conforming to The acid value of the acid value type dispersant is not particularly limited, but is preferably 10 to 200 mg-KOH/g , and the amine value of the amine value type dispersant is not particularly limited, but is 20 to 160 mg-KOH. /g is preferred. Dispersants having an acid value and an amine value greater than 0 are not particularly limited, but preferably have an acid value of 20 to 160 mg-KOH/g and an amine value of 30 to 150 mg-KOH/g .

Surfactant-type dispersants include naphthalenesulfonic acid formalin condensates, aromatic sulfonic acid formalin condensates, anionic surfactants (anionic type) such as polyoxyethylene alkyl phosphates, polyoxyethylene Examples include nonionic surfactants (nonionic type) such as alkyl ethers, and cationic surfactants (cationic type) such as alkylamine salts and quaternary ammonium salts. Various types of surfactant-type dispersants are commercially available, and specific examples thereof are as follows, but are not limited to these.
Kao Corporation: Demol N, RN, MS, SN-B, Emulgen 120, 430, Acetamine 24, 86, Cortamine 24P,
Nikko Chemicals Co., Ltd.: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25,
Daiichi Kogyo Seiyaku Co., Ltd.: PLYSURF AL, A208F,
Lion Corporation: Arcade C-50, T-28, T-50, etc.

Dispersants such as those described above may be used alone or in combination of two or more. When two or more types are combined, for example, in the case of resin type dispersants, different resins are combined, acid value type and amine value type are combined, and in the case of surfactant type dispersants, different ionic properties are combined. (For example, an anionic type and a nonionic type, etc.) may be combined, but not limited to these.

The content (solid content or active ingredient) of the dispersant in the dye dispersion is preferably 10 to 200 parts by weight, more preferably 15 to 150 parts by weight, relative to 100 parts by weight of the water-insoluble dye, from the viewpoint of dispersion stability. preferable. However, the optimum amount of the dispersant to be added may be appropriately adjusted depending on the combination with the type of water-insoluble dye used.

The water is not particularly limited, but preferably contains few impurities, such as ion-exchanged water, distilled water, and ultrapure water. Moreover, you may use the thing which performed the sterilization process.

The content of water in the dye dispersion may be appropriately selected depending on the application, but is generally 200 to 8500 parts by weight per 100 parts by weight of the water-insoluble dye.

The dye dispersion may contain a water-soluble organic solvent in order to improve the wettability of the water-insoluble dye, adjust its solubility, and ensure fluidity. As such a water-soluble organic solvent, those described later can be used. The content thereof is preferably 0.4 to 500 parts by weight per 100 parts by weight of the water-insoluble dye.

In addition to the components described above, the dye dispersion may contain other additives as long as they do not impair the effects described above. Such additives include pH adjusters, antioxidants, ultraviolet absorbers, preservatives, antifungal agents, antifoaming agents, and the like. The content of each of these additives may be used within the range in which they exhibit their functions, but generally 0.1 to 5 parts by weight is preferable for 100 parts by weight of the water-insoluble dye.

A dye dispersion can be produced, for example, as follows.
A dye dispersion can be obtained by mixing each component described above and performing dispersion treatment using a sand mill (bead mill), roll mill, ball mill, paint shaker, ultrasonic disperser, high-pressure emulsifier, or the like.
A case where a sand mill is used will be described as an example. First, each component and beads as a dispersing medium are placed in a sand mill. As the beads, glass beads, zirconia beads, etc. having a particle diameter of 0.01 to 1 mm can be used. The amount of beads used is preferably 2 to 6 weights per weight of the dye dispersion. After that, the sand mill is operated to carry out dispersion treatment. Dispersion treatment conditions are preferably about 1000 to 2000 rpm for 1 to 20 hours. After the dispersing treatment, the beads are removed by filtration or the like to obtain a dye dispersion.

By using the dye derivative having the structure represented by formula (1), the dye dispersion can stably maintain the dispersed state of the particles containing the water-insoluble dye. That is, as will be described later, it is possible to effectively prevent the particles in the dye dispersion from aggregating during storage and increasing the average particle size. In addition, sedimentation of particles can be effectively suppressed.

(water-based ink)
A water-based ink according to an embodiment of the present invention contains the above-described water-based dye dispersion for water-based ink and a surfactant. By using the dye dispersion in this way, it is possible to effectively suppress the increase in the average particle size due to aggregation of particles during storage even as an aqueous ink.

The content of the dye dispersion can be appropriately determined depending on the application, etc., but from the viewpoint of coloring power, the content of the water-insoluble dye relative to the total weight of the ink is 0.1 to 10% by weight. A dispersion is preferably included.

The surfactant is not particularly limited, and surfactants commonly used in water-based inks can be used. Surfactants can increase the wettability of the base material and improve the permeability of the water-based ink. From the viewpoint of ionicity, such surfactants may be anionic, cationic, amphoteric, or nonionic. Further, from the viewpoint of improving ink ejection responsiveness in ink-jet printing, silicone-based surfactants, fluorine-based surfactants, and the like are preferable.

Examples of anionic surfactants include alkylsulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and their salts, N-acylmethyltaurate salts, alkyl sulfate polyoxyalkyl Ether sulfate, alkyl sulfate, polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol type phosphate, alkyl type phosphate, alkylaryl sulfonate, diethyl sulfo amber acid salts, diethylhexylsulfosuccinates, dioctylsulfosuccinates, and the like.

Cationic surfactants include 2-vinylpyridine derivatives, poly-4-vinylpyridine derivatives and the like.

Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. is mentioned.

Nonionic surfactants include ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Esters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol acetylene glycol (alcohol)-based;

Examples of silicone surfactants include unmodified polyorganosiloxane, ether-modified polyorganosiloxane, ester-modified polyorganosiloxane, epoxy-modified polyorganosiloxane, amine-modified polyorganosiloxane, carboxyl-modified polyorganosiloxane, fluorine-modified polyorganosiloxane, Alkyloxy-modified polyorganosiloxane, mercapto-modified polyorganosiloxane, (meth)acrylic-modified polyorganosiloxane, phenol-modified polyorganosiloxane, phenyl-modified polyorganosiloxane, carbinol-modified polyorganosiloxane, or aralkyl-modified polyorganosiloxane. .
These silicone-based surfactants may be synthesized or purchased commercially. Commercial products include, for example, BYK-306, 307, 333, 337, 341, 345, 346, 347, 348, 349, 378 (manufactured by BYK-Chemie Japan Co., Ltd.), KF-351A, 352A, 353, 354L , 355A, 615A, 945, 640, 642, 643, 6011, 6012, 6015, 6017, 6020, X-22-4515 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., but not limited to these do not have.

Examples of fluorine compound-based surfactants include those having a perfluoroalkyl group. Examples of such surfactants include, but are not limited to, Megafac 144D manufactured by DIC Corporation, Surflon S-141, 145, and Surflon S-131, 132, 211 manufactured by Asahi Glass Co., Ltd. do not have.

The above surfactants may be used alone or in combination of two or more.

The content of the surfactant in the water-based ink can be appropriately selected according to the application, etc., but from the viewpoint of wettability to the colored substrate and ink miscibility in the water-based ink, 0.1 to 5% by weight.

Water may be added to the water-based ink to adjust the concentration of the water-insoluble dye. The amount of water to be added can be appropriately determined according to the use of the water-based ink. preferable. As the water, water that can be used in the dye dispersion can be used as described above.

Water-based inks may contain other additives besides the dye dispersion and surfactant, and optionally additional water. Examples of such additives include water-soluble organic solvents, pH adjusters, chelating reagents, rust inhibitors, antioxidants, ultraviolet absorbers, antiseptics, antifungal agents, antifoaming agents, and the like. The content of each of these additives may be used within the range in which their functions are exhibited.

The water-soluble organic solvent is not particularly limited, and includes monohydric alcohols such as methanol, ethanol, and isopropyl alcohol; polyhydric alcohols; ketones or ketoalcohols such as acetone and diacetone alcohol; Ethers are included. Among these, polyhydric alcohols are preferable from the viewpoint of suppressing volatilization and preventing solidification of ink in an inkjet printing apparatus. Examples of such polyhydric alcohols include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, oxyethylene or oxypropylene addition polymers such as polypropylene glycol; ethylene glycol, propylene; Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as glycol, trimethylene glycol, butylene glycol, and hexylene glycol; triols, such as 1,2,6-hexanetriol; thiodiglycol; mentioned.
The content of the water-soluble organic solvent is preferably 1 to 40% by weight with respect to the total weight of the water-based ink.

The pH adjuster is not particularly limited as long as it is a compound capable of adjusting the pH of the water-based ink in the range of 6 to 11. Examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine and diethylethanolamine; aqueous ammonia; and the like.
The content of the pH adjuster is preferably 0.1 to 5% by weight with respect to the total weight of the aqueous ink.

The water-based ink can be obtained by charging a dye dispersion, a surfactant, and optionally water and the above-mentioned additives into a stirring device and stirring them according to a standard method.

The water-based ink thus obtained contains the dye dispersion obtained using the dye derivative described above, so that the aggregation of particles in the water-based ink is effective even in the presence of other components contained in the water-based ink. stable storage is possible. Also, even if direct textile printing is performed, it is possible to realize the same color tone of the printed matter as in the case where the dye derivative is not used or in the case where the dye derivative is not sublimated and not transferred to the printed matter as in sublimation type printing.

Since the water-based ink can be stored stably in this way, it can be applied to various uses. For example, recording ink for home and office printers, copiers and facsimiles, papers such as catalogs, magazines and package labels, metal products such as cans, ceramic products such as tiles, resin products such as films, etc. It can be suitably used as a printing ink (or recording ink) for colored substrates such as textile products such as fabrics. In particular, since it is possible to suppress the aggregation of particles in water-based ink, even after ink is filled, the aggregation of particles is suppressed and stable storage is possible, so the ejection stability is high. preferred. In addition, regarding printing on textile products such as textiles by an inkjet method, the aforementioned water-based inks are particularly suitable as water-based inks for direct textile printing that directly print on textiles that are coloring substrates. Of course, it may also be used as a sublimation-type water-based textile printing ink for printing on paper used for sublimation-type thermal transfer onto a fabric or on an intermediate recording medium that is a colored resin base material.

Hereinafter, embodiments of the present invention will be described in more detail based on examples.

(Production Example 1) Production of Dye Derivative 1 Chlorosulfonic acid: 250 parts by weight, C.I. I. Disperse Yellow 82 (manufactured by Nippon Kayaku Co., Ltd., kayaset yellow SF-G): 33.3 parts by weight and thionyl chloride: 11.9 parts by weight were mixed and reacted by stirring at 100° C. for 20 hours. The resulting reaction solution was mixed with a large amount of cold water to precipitate crystals. The obtained crystals were separated by filtration and washed with pure water to obtain a reddish-orange aqueous paste. This paste was dispersed in 1000 parts by weight of cold water, mixed with 52.1 parts by weight of diethylaminopropylamine, and stirred at 20° C. for 15 hours to react. Then, it was separated by filtration, washed with pure water, and dried at 80° C. to obtain a dye derivative 1:44.7 parts by weight.

Identification of the chemical structure of the obtained dye derivative 1 was carried out using an AXIMA-CFR plus type matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOF-MS) manufactured by Shimadzu Corporation. -4-Hydroxycinnamic acid (CHCA) was used as a matrix and measured in positive ion mode. As a result, a molecular ion peak was observed at m/z=525. In formula (4), R ¹ is a group represented by —N(C ₂ H ₅ ) ₂ , R ² is a group represented by formula (2), and R ³ is —NH—C ₃ The group H ₆ —N(C ₂ H ₅ ) ₂ , corresponding to monoisotopic masses corresponding to n=1.

(Production Example 2) Production of dye derivative 2 22% fuming sulfuric acid: 292 parts by weight, C.I. I. Disperse Yellow 232 (Macrolex Fluorescent Yellow 10GN manufactured by Lanxess): 38.4 parts by weight were mixed and reacted by stirring at 80°C for 24 hours. The resulting reaction solution was mixed with a large amount of cold water to precipitate crystals. The obtained crystals were separated by filtration and washed with a 10% sodium sulfate aqueous solution to obtain an orange water paste. This paste was dried at 80° C. to obtain 58.5 parts by weight of solid matter.

The obtained solid matter: 44.8 parts by weight, chlorosulfonic acid: 250 parts by weight, and thionyl chloride: 25.1 parts by weight were mixed and reacted by stirring at 85°C for 3 hours. The resulting reaction solution was mixed with a large amount of cold water to precipitate crystals. After the obtained crystals were separated by filtration, they were washed with pure water to obtain a yellow watery paste. This paste was dispersed in 1000 parts by weight of cold water, mixed with 130.2 parts by weight of diethylaminopropylamine, and stirred at 20° C. for 15 hours to react. Then, it was separated by filtration, washed with pure water, and dried at 80° C. to obtain dye derivative 2: 44.0 parts by weight.

When the chemical structure of the obtained dye derivative 2 was identified in the same manner as in Production Example 1, a molecular ion peak was observed at m/z=560. In formula (4), R ¹ is a group represented by —N(C ₂ H ₅ ) ₂ , R ² is a group represented by formula ( 3 ), and R ⁴ and R ⁶ , R ⁷ is a hydrogen atom, R ⁵ is a group represented by a chlorine atom, R ³ is a group represented by —NH—C ₃ H ₆ —N(C ₂ H ₅ ) ₂ , n is a mono Matches isotopic masses.

(Example 1)
C.I. I. Disper Yellow 114 (Oil Yellow DY-572 manufactured by Arimoto Chemical Industry Co., Ltd.): 13.5% by weight, dye derivative 1 obtained in Production Example 1: 1.5% by weight, resin type dispersant (manufactured by BYK, Disperbyk 190, solid content 40%, acid value 10 mg-KOH/g): 3% by weight (solid content), ion-exchanged water: balance, 0.3 mm diameter zirconia beads: 460 parts by weight were charged into a sand mill and run at 1500 rpm for 15 hours. Distributed processing was performed. After that, the zirconia beads were removed to obtain a water-based dye dispersion. The composition of the resulting water-based dye dispersion is shown in Table 1.

(Example 2)
An aqueous dye dispersion was obtained in the same manner as in Example 1, except that the dye derivative 2 obtained in Production Example 2 was used instead of the dye derivative 1. The composition of the resulting water-based dye dispersion is shown in Table 1.

(Example 3)
C. I. Instead of Disperse Yellow 114, C.I. I. A water-based dye dispersion was obtained in the same manner as in Example 1, except that Disperse Yellow 232 (Macrolex Fluorescent Yellow 10GN, manufactured by LANXESS) was used. The composition of the resulting water-based dye dispersion is shown in Table 1.

(Example 4)
C. I. Instead of Disperse Yellow 114, C.I. I. A water-based dye dispersion was obtained in the same manner as in Example 2, except that Disperse Yellow 232 (Macrolex Fluorescent Yellow 10GN, manufactured by LANXESS) was used. The composition of the resulting water-based dye dispersion is shown in Table 1.

(Comparative example 1)
C. I. An aqueous dye dispersion was obtained in the same manner as in Example 1, except that the content of Disperse Yellow 114 was changed from 13.5% by weight to 15% by weight, and Dye Derivative 1 was not used. The composition of the resulting water-based dye dispersion is shown in Table 1.

(Comparative example 2)
C. I. An aqueous dye dispersion was obtained in the same manner as in Example 3, except that the content of Disperse Yellow 232 was changed from 13.5% by weight to 15% by weight, and Dye Derivative 2 was not used. The composition of the resulting water-based dye dispersion is shown in Table 1.

(evaluation)
Water-based inks were prepared using the water-based dye dispersions of Examples and Comparative Examples, and the following evaluations were performed on the water-based inks. The evaluation results are shown in Table 1.

<Production of water-based ink>
Aqueous dye dispersion obtained in Examples and Comparative Examples: 3 g, surfactant (BYK-348 manufactured by BYK): 0.1 g, glycerin: 2 g, propylene glycol: 1 g, ion-exchanged water: 3 g mixed, Stir to prepare a water-based ink.

<Stability test>
Ink stability is an accelerated evaluation of the susceptibility to aggregation of particles in water-based ink during storage, using the rate of increase in particle size as an index.
10 g of each prepared water-based ink was placed in a sealed container and allowed to stand at 60° C. for one week. After cooling to room temperature, the average particle size (A) of the particles in the aqueous ink was measured using a dynamic light scattering photometer (ELS-8000, manufactured by Otsuka Electronics Co., Ltd.). The stability was evaluated by the rate of increase with respect to the average particle size (B) measured in the same manner before standing at 60°C. The rate of increase (%) was calculated by the following formula.
Increase rate (%) = (A - B) / B x 100
Evaluation criteria are as follows.
○: Increase rate of average particle size is less than 10% △: Increase rate of average particle size is 10% or more and less than 20% ×: Increase rate of average particle size is 20% or more

<Color development test>
Prepared water-based ink: 2 g is spread on a polyester fabric (manufactured by Teijin Limited, Polyester Tropical) with a 0.15 mm bar coater, dried overnight at room temperature, and then heated at 200 ° C. for 1 minute. and colored. The surface of the fabric printed with aqueous ink is measured using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product name CM-3700d) by the specular reflection light removal (SCE) method, L *, a *, b * was measured, and the color difference ΔE was calculated. For Examples 1 and 2, the difference (ΔE) from Comparative Example 1 was calculated, and for Examples 3 and 4, the difference (ΔE) from Comparative Example 2 was calculated. Table 1 shows the results.

As shown in Table 1, it can be seen that the use of a specific dye derivative provides good ink stability, and even when direct printing is performed, the same level of color tone is obtained as when no dye derivative is used.

Claims (5)

A water-based dye dispersion for water-based inks, comprising a dye derivative represented by the following formula (1), a water-insoluble dye, a dispersant, and water.

(In formula (1), R ¹ represents an amino group, R ² represents a group represented by the following formula (2) or (3), and R ³ represents —NH —R ⁸ —NR ⁹ R ^{10 )} . R ⁸ represents an alkylene group or phenylene group having 1 to 4 carbon atoms, R ⁹ and R ¹⁰ represent independently selected alkyl groups having 1 to 4 carbon atoms, n is 0 Indicates a real number larger than 2.)

(In formula (2), * indicates a bond.)

(In Formula (3), R ⁴ to R ⁷ independently represent a hydrogen atom or a halogen atom. * represents a bond.) 2. The aqueous dye dispersion for water-based ink according to claim 1, wherein the dye derivative represented by the formula (1) is a dye derivative represented by the following formula (4).

R ¹ in formula (1) is —NH ₂ , —NHR ⁸ (wherein R ⁸ represents a hydrocarbon group having 1 to 4 carbon atoms) and —NR ⁹ R ¹⁰ (wherein R ⁹ , 3. The water-based dye dispersion for water-based ink according to claim 1, wherein each R ¹⁰ independently represents a hydrocarbon group having 1 to 4 carbon atoms. An aqueous ink comprising the aqueous dye dispersion for aqueous ink according to any one of claims 1 to 3 and a surfactant. 5. The water-based ink according to claim 4, which is used for recording by an inkjet system.