JP7084089B2 - Blue dye composition - Google Patents

Description

The present invention relates to a blue dye composition containing an anthraquinone-based compound, a substrate to which the blue dye composition is attached (particularly polyester fiber), and a dyeing method.

Disperse dyes are widely used industrially as dyes for dyeing hydrophobic fibers such as polyester. Examples of the fiber dyeing method include mass production method industrial dyeing methods that have been conventionally carried out such as dyeing, printing, and continuous dyeing. Further, in recent years, printing by the inkjet method is increasing in order to cope with small lots of various kinds, shortening of delivery time, digitization of designs, and the like.
Textile printing methods using inks containing disperse dyes can be broadly divided into two. One method is "direct printing", in which ink is attached to the fibers. Another way is
This is "sublimation transfer printing" in which the dye is sublimated from the intermediate medium to the fibers and printed by adhering the ink to an intermediate medium such as paper and then superimposing the ink adhering surface on the fibers and heating them. .. The sublimation transfer printing method can dry-heat adhere the dye to the fiber and does not require a cleaning step after dyeing. For this reason, the sublimation transfer printing method can significantly reduce water such as dyeing waste water in the dyeing process. For this reason, this printing method is becoming more and more popular not only in developed countries but also in emerging countries as an environmentally friendly dyeing method.
Fibers printed with disperse dyes are generally known to have very good sharpness and fastness. For this reason, it is expected to be applied to various applications such as sign displays, sports apparel, interiors, and car seats. Therefore, the disperse dye is required to be clear, have a wide color reproduction range, and have good light resistance. Further, among the disperse dyes, the dye used for sublimation transfer printing is required to have good sublimation transferability (dyeing property) in addition to these.
Among the yellow, magenta, and cyan disperse dyes used for full-color printing, the cyan dye is an anthraquinone compound, for example, C.I. I. Disperse blue 60, 334, and 359 and the like can be mentioned. Among these, C.I. I. Although Disperse Blue 60 and 334 have high light resistance, they have low sublimation transferability, and there is a problem that a high staining concentration cannot be obtained. In addition, C.I. I. Although Disperse Blue 359 has high sublimation transferability, it has a problem that it has low light resistance and is discolored to reddish by light. Therefore, there is a strong demand for the development of dyes having high light resistance and good sublimation transferability. However, at present, no dye that can satisfy this requirement has been found.

Patent Documents 1 and 2 disclose a dispersion dye mixture.

U.S. Pat. No. 8,506,654 Japanese Unexamined Patent Publication No. 2004-339514

INDUSTRIAL APPLICABILITY The present invention is a blue dye composition having good light resistance and used for dyeing various base materials, preferably fibers, more preferably polyester fibers, or blended fibers containing polyester fibers, preferably blue having sublimation transferability. The subject is to provide a dye composition.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a specific blue dye composition, and have completed the present invention. That is, the present invention relates to the following 1) to 12).

1)
A compound represented by the following formula (1) and a colorant A having a chemical structure different from that of the compound represented by the following formula (1) and having a maximum absorption wavelength in the range of 550 nm to 700 nm. The blue dye composition contained.

[In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1-C4 alkyl group, and all of R ¹ , R ² and R ³ are hydrogen atoms. There is no such thing. X represents an oxygen atom or an imino group. ]
2)
In the formula (1), R ¹ is a hydrogen atom or a C1-C4 alkyl group, R ² is a C1-C4 alkyl group, R ³ is a C1-C4 alkyl group, and X is an oxygen atom. The blue dye composition according to 1) above.
3)
In the above formula (1), R ¹ is a hydrogen atom, R ² is a C1-C4 alkyl group, R ³ is a C1-C4 alkyl group, and X is an oxygen atom, according to the above 1). Blue dye composition.
4)
In the above formula (1), R ¹ is a hydrogen atom, R ² is a C1-C4 alkyl group, R ³ is a C1-C4 alkyl group, and the total number of carbon atoms of R ² and R ³ is The blue dye composition according to 1) above, wherein the composition is 4 to 8 and X is an oxygen atom.
5)
The colorant A is C.I. I. Disperse Blue, C.I. I. Disperse Violet, and C.I. I. The blue dye composition according to 1) above, which is a dye selected from Solvent Blue.
6)
An ink containing at least one liquid medium selected from water and an organic solvent, and the blue dye composition according to any one of 1) to 5) above.
7)
The ink according to 6) above, which further contains a dispersant.
8)
A base material to which the blue dye composition according to any one of 1) to 5) above is attached.
9)
A base material to which the ink according to 6) or 7) is attached.
10)
The base material according to 8) or 9) above, wherein the base material is a fiber.
11)
The base material according to the above 10), wherein the fiber is a hydrophobic fiber.
12)
The base material according to 11) above, wherein the hydrophobic fiber is polyester or a blended fiber containing polyester.

According to the present invention, it has good light resistance and has a blue dye composition, preferably sublimation transferability, which is used for dyeing various base materials, preferably fibers, more preferably polyester fibers, or blended fibers containing polyester fibers. A blue dye composition could be provided.

As used herein, "CI" means "color index". Further, in the present specification, "%" and "part" including Examples and the like are described in terms of mass unless otherwise specified.
Further, the blue dye composition may be simply referred to as a "dye composition" unless otherwise specified in the present specification.

In the formula (1), examples of the C1-C4 alkyl group in R ¹ , R ² and R ³ include a linear, branched chain, or cyclic alkyl group. Among these, straight chains or branched chains are preferable, and straight chains are more preferable.
Specific examples thereof include linear alkyl groups of methyl, ethyl, n-propyl and n-butyl; branched chain alkyl groups of isopropyl, isobutyl, sec-butyl and t-butyl; cyclic alkyl groups of cyclopropyl and cyclobutyl. Can be mentioned. Of these, ethyl is preferred.
The total number of carbon atoms of R ¹ , R ² and R ³ is usually 4 to 12, preferably 4 to 8, more preferably 4 to 6, still more preferably 4 or 5, and particularly preferably 4. The smaller the total number of carbon atoms, the better the sublimation transferability tends to be. Focusing on the sublimation transferability, the total number of carbon atoms of R ¹ and R ² is preferably 4 or 5, and more preferably 4. The compound represented by the formula (1) preferably has sublimation transferability.
For R ¹ , R ² and R ³ , all are alkyl groups, or any one is preferably a hydrogen atom and the other two are preferably alkyl groups; one is a hydrogen atom and the other two are alkyl. The group is more preferable.

X is an oxygen atom or an imino group, and an oxygen atom is preferable.

The compound represented by the formula (1) can be obtained by a known method.
As an example, the compound represented by the following formula (4) and the amine compound represented by the following formula (5) are added in an organic solvent (for example, sulfolane), and the temperature is 70 ° C to 220 ° C, preferably 120 ° C to 180. By reacting at ° C, the compound represented by the above formula (1) can be obtained. This reaction can be carried out under normal pressure. Further, it is preferable to carry out the reaction under pressure using an autoclave or the like because the reaction is promoted.

In equation (3), X has the same meaning as in equation (1).

In equation (5), R ¹ , R ² and R ³ have the same meaning as in equation (1).

The compound obtained as described above can be purified by a known method, if necessary. Examples of the purification method include acidification, salting out, suspension purification, and crystallization.

The colorant A is preferably a colorant having a chemical structure different from that of the compound represented by the formula (1) and having a maximum absorption wavelength (λmax). The colorant A usually has a maximum absorption wavelength of 550 nm to 700 nm, preferably 580 nm to 630 nm.
The colorant A is preferably a water-insoluble dye; C.I. I. Disperse Violet, C.I. I. Disperse Blue, and C.I. I. Dyes selected from Solvent Blue are more preferred.
Specific examples thereof include, for example, C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57; C.I. I. Disperse Blue 3, 5, 7, 9, 14, 16, 19, 20, 26, 27, 28, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 77, 79, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 134, 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, 266, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 334, 359, 360, 366; C.I. I. Examples include Solvent Blue 35, 36, 59, 63, 83, 97, 104, 105, 111 and the like.

As the colorant A, a compound represented by the following formula (2) is also preferable.

In equation (2),
^R4 represents a hydrogen atom, a phenyl group which may have a substituent, or an alkyl group.
R ⁵ represents a hydrogen atom, a phenyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, or a halogen atom.
R ⁶ represents a hydrogen atom, a phenyl group which may have a substituent, an alkoxy group which may have a substituent, an aminocarbonyl group which may have a substituent, or a halogen atom.
Q represents an oxygen atom or an NH group.
R ⁷ represents a hydrogen atom when Q is an oxygen atom, and represents a hydrogen atom when Q is an NH group, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
R ⁸ represents a hydrogen atom, an amino group which may have a substituent, a nitro group, or a hydroxy group.
R ⁹ represents a hydrogen atom, an amino group, a nitro group, or a hydroxy group.
However, not all of R ⁴ to R ⁹ become hydrogen atoms.

Examples of the substituent of the phenyl group which may have a substituent in ^R4 include an alkyl group and an alkylsulfonyloxy group.
Among the above, examples of the alkyl group include a straight chain, a branched chain, or a cyclic alkyl group, and a straight chain or a branched chain is preferable, and a straight chain is more preferable. Its carbon number range is usually C1-C3, preferably C1-C2. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl and cyclopropyl. Of these, methyl is preferred.
Among the above, examples of the alkylsulfonyl group include a sulfonyloxy group having the alkyl group. Specific examples thereof include methyl sulfonyl oxy, ethyl sulfonyl oxy, n-propyl sulfonyl oxy, isopropyl sulfonyl oxy, and cyclopropyl sulfonyl oxy. Of these, methylsulfonyloxy is preferred.
Specific examples of the phenyl group which may have a substituent in ^R4 include, for example, phenyl, 3-methylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, 2,6-diethyl-4-. Examples thereof include methylphenyl and 4-methylsulfonyloxyphenyl.

Examples of the alkyl group in ^R4 include a straight chain, a branched chain, or a cyclic unsubstituted alkyl group, and a straight chain or a branched chain is preferable. Its carbon number range is usually C1-C5, preferably C1-C4. Specific examples thereof include methyl, ethyl, n-propyl, n-butyl, isopropyl and the like.

^Examples of the substituent of the phenyl group which may have the substituent in R5 and ^R6 include an alkyl group, an alkoxy group, or a hydroxy group. Among these, a hydroxy group is preferable in ^R5 , and an alkoxy group or a hydroxy group is preferable in ^R6 .
Examples of the alkyl group include the alkyl group mentioned above as “the substituent of the phenyl group which may have the substituent in ^R4 ” and the same alkyl group including preferable ones.
Examples of the alkoxy group include a straight chain, a branched chain, or a cyclic alkyloxy group, and a straight chain or a branched chain is preferable, and a straight chain is more preferable. The range of the number of carbon atoms is usually C1-C3, preferably C1-C2, and more preferably C1. Specific examples of the alkoxy moiety include methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy and the like.
Specific examples of the phenyl group which may have a substituent in R ⁵ and R ⁶ include, for example, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4 -Ethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl and the like can be mentioned. Among these, 4-hydroxyphenyl is preferable for R5, and ⁴ -methoxyphenyl and ⁴ -hydroxyphenyl are preferable for R6.

^Examples of the alkoxy group which may have a substituent in R5 and ^R6 include an alkyloxy group and a phenyloxy group which may have a substituent, respectively. Of these, the phenyloxy group is preferably unsubstituted.
Examples of the alkyloxy group include a straight chain, a branched chain, or a cyclic alkyloxy group, and a straight chain or a branched chain is preferable, and a straight chain is more preferable. Its carbon number range is usually C1-C7, preferably C1-C6. Specific examples of the alkyloxy group include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, isopropoxy, cyclopropoxy and the like.
^Examples of the substituent of the alkoxy group which may have a substituent in R5 include an alkyloxy group and a hydroxy group. Of these, hydroxy groups are preferred.
Moreover, as a substituent of the alkoxy group which may have a substituent in ^R6 , a phenyloxy group can be mentioned.
Specific examples of alkoxy groups that may have substituents ^on R5 and R6 include, for example, ² -hydroxy-n-ethoxy, 3-hydroxy-n-propoxy, 4-hydroxy-n-butoxy, 5-. Examples thereof include hydroxy-n-pentoxy, 6-hydroxy-n-hexyloxy, phenyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-hydroxyphenyloxy and the like. Among these, ⁶ -hydroxy-n ^- hexyloxy or phenyloxy is preferable in R5, and a phenyloxy group is preferable in R6.

^Examples of the alkylthio group which may have a substituent in R5 include a straight chain, a branched chain, or a cyclic alkylthio group, and a straight chain or a branched chain is preferable, and a straight chain is more preferable. Its carbon number range is usually C1-C4, preferably C1-C3, more preferably C2. Specific examples thereof include methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, isopropylthio, cyclopropylthio and the like.
^Examples of the substituent of the alkylthio group which may have a substituent in R5 include an alkoxy group and a hydroxy group. Of these, hydroxy groups are preferred. Specific examples of the alkoxy group include the ^same alkoxy group as mentioned above as “the substituent of the phenyl group which may have a substituent in R5”, including preferable ones.
Specific examples of the alkylthio group which may have a substituent in R5 include, for example, methylthio, ethylthio, n ^- propylthio, isopropylthio, cyclopropylthio, 2-methoxyethylthio, 3-methoxypropylthio, 2-. Examples thereof include hydroxyethylthio and 3-hydroxypropylthio. Of these, 2-hydroxyethylthio is preferred.

Examples of the halogen atom in ^R5 and ^R6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a chlorine atom and a bromine atom are more preferable.

Examples of the substituent of the aminocarbonyl group which may have a substituent in ^R6 include a linear, branched chain, or cyclic hydroxyalkyl group. Among these, straight chains or branched chains are preferable, and straight chains are more preferable. The range of the number of carbon atoms is usually C2-C6, preferably C2-C4, and more preferably C2.
Specific examples of the hydroxyalkyl group include 2-hydroxyethyl, 3-hydroxy-n-propyl, 4-hydroxy-n-butyl, 5-hydroxy-n-pentyl, 6-hydroxy-n-pentyl and the like. Of these, 2-hydroxyethyl is preferred.
As the aminocarbonyl group which may have a substituent in R6, an unsubstituted aminocarbonyl or a ² -hydroxyethylaminocarbonyl is preferable.

When Q is an NH group, the compound represented by the formula (2) means the compound represented by the following formula (3). In the following formula (3), R ⁴ to R ⁹ have the same meaning as the formula (2).

When Q is an NH group, examples of the alkyl group which may have a substituent in R ⁷ include an unsubstituted alkyl group and a hydroxyalkyl group. Further, examples of the phenyl group which may have a substituent include a phenyl group having an alkyl group among the above-mentioned "substituents of a phenyl group which may have a substituent in ^R4 ".
^Examples of the alkyl group which may have a substituent include the unsubstituted alkyl group mentioned as "alkyl group in ^R4 " and the substituent in "R6" including preferable ones. The same as the hydroxyalkyl group mentioned as "a substituent of a good aminocarbonyl group" can be mentioned.
Preferred specific examples of R ⁷ include methyl, ethyl, n-propyl, n-butyl, isopropyl, 2-hydroxyethyl, 2,4,6-trimethylphenyl, 2,6-diethyl-4-methylphenyl and the like.

Examples of the amino group which may have a substituent in R ⁸ include the unsubstituted alkyl group mentioned as “alkyl group in R ⁴ ” among the above, including preferable ones. Among them, methyl is preferable.

Among the above, the colorant A is C.I. I. Disperse Violet, and C.I. I. A compound selected from Solvent Blue and represented by the above formula (2) or formula (3) is preferable.
Such compounds include, for example, C.I. I. Disperse Blue 3, 5, 14, 26, 28, 35, 56, 60, 72, 73, 77, 81, 334; C.I. I. Disperse Violet 27 and the like can be mentioned.

Specific examples of compounds preferable as the colorant A are shown in Tables 1 and 2 below.

In the above, as the colorant A, C.I. I. Disperse Violet 27, and C.I. I. Disperse Blue 72 is preferred, C.I. I. Disperse Blue72 is more preferred.

The ratio of the content of the compound represented by the formula (1) to the content of the colorant A contained in the dye composition is usually 10/90 to 90/10, preferably 30/70 to 90/10 on a mass basis. 10, more preferably 40/60 to 85/15, still more preferably 55/45 to 80/20. By setting this ratio, the hue and sublimation property can be improved.

The dye composition can be an ink containing a liquid medium and the dye composition. As the liquid medium, at least one selected from water and an organic solvent is preferable.
The dye mixture may be a water-based ink containing water and, if necessary, an organic solvent, or an ink substantially free of water, that is, a solvent ink. As used herein, the term "substantially water-free ink" means an ink to which water is not intentionally added.

Examples of the organic solvent include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol; N, N-dimethylformamide, N, N-dimethyl. Amids such as acetoamides; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidine-2-one or 1,3-dimethylhexahydropyrimido-2-one. Heterocyclic ketones such as: acetone, methyl ethyl ketone, ketones such as 2-methyl-2-hydroxypentane-4-one or keto alcohols; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2-propanediol, 1, 3-Propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol , 1,6-Hexanediol, etc .; di, oligo, or polyalkylene having C2-C6 alkylene units such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, etc. Glycol or thioglycol; polyols such as glycerin, hexane-1,2,6-triol, trimethylolpropane (preferably triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples thereof include C1-C4 monoalkyl ethers of polyhydric alcohols such as monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; γ-butyrolactone; dimethyl sulfoxide and the like.

When the ink is a water-based ink, it is preferable to further contain a dispersant. The organic solvent at that time is preferably a water-soluble organic solvent. That is, when the ink is a water-based ink, an ink containing water, a water-soluble organic solvent, a dispersant, a compound represented by the formula (1), and a colorant A is preferable.

The compound represented by the formula (1) and a part or all of the colorant A can be coated with a dispersant.
Examples of the dispersant include a nonionic dispersant, an anion dispersant, and a polymer dispersant, which can be appropriately selected depending on the intended purpose.
The amount of the dispersant used is usually 1% to 100%, preferably 5% to 90%, and more preferably 10% to 80% with respect to the total mass of the dye composition in terms of solid content.

Nonionic dispersants include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, and sorbitan ester polyoxy. Ethylene ether, polyoxyethylene ether of sorbitol ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, amine oxide, polyoxyethylene alkylamine, polyoxyethylene-β-naphthyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene di Examples include styrylphenyl ether and the like.

Anion dispersants include alkyl sulfates, alkyl ether sulfates, alkyl ester sulfates, alkylaryl ether sulfates, alkyl sulfonates, sulfosuccinates, alkylaryl and alkylnaphthalene sulfonates, alkyl phosphates, polys. Examples thereof include oxyethylene alkyl ether phosphate ester salt, alkyl allyl ether phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrylphenyl ether sulfate, polyoxyethylene distyryl phenyl ether sulfate and the like.
Further, a polymer-based sulfonic acid, preferably a formalin condensate of aromatic sulfonic acid, a formalin condensate of lignin sulfonic acid, and the like can also be mentioned. Examples of the formalin condensate of aromatic sulfonic acid include cleosort oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, β-naphthol sulfonic acid, β-naphthalin sulfonic acid and β-naphthol sulfonic acid, and cresol sulfonic acid. Examples thereof include formalin condensates of 2-naphthol-6-sulfonic acid. Among these, creosote oil sulfonic acid, naphthalene sulfonic acid, lignin sulfonic acid, each formalin condensate and the like are preferable.
Such anion dispersants are, for example, Demol N, Demol C, Demol SNB, Demol W manufactured by Kao Corporation, and Labelin W (formalin condensate of creosote oil sulfonic acid) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. It can be obtained as such.
The anion dispersant can also be used as a salt in which a functional group such as sulfonic acid is neutralized with a neutralizing agent. As the neutralizing agent, a pH adjusting agent or the like described later can be used.

The polymer dispersant includes styrene and its derivatives (preferably monomers selected from styrene and α-methylstyrene); vinylnaphthalene and its derivatives; aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids. Etc .; (meth) acrylic acid and its derivatives; maleic acid and its derivatives; itaconic acid and its derivatives; fumaric acid and its derivatives; vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and its derivatives. Examples thereof include a copolymer composed of at least two monomers (preferably at least one of which is a hydrophilic monomer) selected from the body, and / or salts thereof. Examples of the copolymer include block copolymers, random copolymers, graft copolymers and the like. In addition, in this specification, (meth) acrylic acid means both methacrylic acid and acrylic acid.
Among these, a copolymer composed of at least two monomers selected from styrene and its derivative and (meth) acrylic acid and its derivative is preferable. As a specific example of such a dispersant, for example, the John Krill series manufactured by BASF is preferable.

As a method for preparing a dispersion liquid (preferably an aqueous dispersion liquid) containing the above compound, a known method can be used. As an example, there is a method of mixing the dye mixture and a dispersant and performing a dispersion treatment using a sand mill (also referred to as a bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer or the like. Of these, sand mills are preferred. For the preparation of the dispersion liquid using a sand mill, it is preferable to use beads having a diameter of about 0.01 mm to 1 mm. Further, in the preparation of the dispersion liquid, the efficiency of dispersion can be improved by increasing the filling rate of beads and the like.
After the dispersion treatment, beads, impurities, etc. are removed by filtration and / or centrifugation. At this time, it is also preferable to remove particles larger than the target average particle size. By removing such particles, clogging of the printer head can be prevented.
If foaming occurs during the preparation of the dispersion, a very small amount of a known silicone-based or acetylene glycol-based defoaming agent can be added.
Other methods for preparing the dispersion include acid analysis method, phase inversion emulsification method, interfacial polymerization method, in-situ polymerization method, in-liquid curing coating method, core selvation (phase separation) method, in-liquid drying method, and melting. Dispersion cooling method, air suspension coating method, spray drying method and the like can be mentioned. Among these, the phase inversion emulsification method, the acid analysis method, and the interfacial polymerization method are preferable.

The ink may contain an ink preparation agent, if necessary. Examples of the ink preparation agent include antiseptic and antifungal agents, pH adjusters, chelating reagents, rust preventives, ultraviolet absorbers, viscosity regulators, dye dissolving agents, fading inhibitors, surface tension regulators, defoamers and the like. Can be mentioned. The total content of the ink preparation agent is usually about 0 to 10%, preferably about 0.05 to 5%, based on the total mass of the ink.

Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, zincpyridinethion-1-oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-. Examples thereof include 3-one amine salt and Proxel GXL manufactured by Arch Chemicals.

As the pH adjuster, any substance can be used as long as the pH of the ink can be controlled to about 6 to 11. For example, the alcohol amines, alkyl amines; hydroxides and carbonates of Group 1 elements in the periodic table of elements such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, etc.; Examples thereof include aminosulfonic acids such as taurine.

Examples of the chelating reagent include sodium ethylenediamine tetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like.

Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds. Further, a fluorescent whitening agent such as a benzoxazole compound can also be used as an ultraviolet absorber.

Examples of the viscosity adjusting agent include the above-mentioned water-soluble organic solvent and water-soluble polymer compound. Examples of the latter include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines and the like.

Examples of the dye dissolving agent include urea, ε-caprolactam, ethylene carbonate and the like.

Anti-fading agents are used for the purpose of improving the storage stability of images. As the anti-fading agent, various organic and metal complex-based anti-fading agents can be used.
Examples of the organic system include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilins, heterocycles and the like.
Examples of the metal complex system include nickel complexes and zinc complexes.

Examples of the surface tension adjusting agent include a surfactant. Examples of the type of surfactant include anion, cation, amphoteric, nonionic, silicone-based, and fluorine-based.

As anionic surfactants, alkyl sulfosulphonates; α-olefin sulfonates; polyoxyethylene alkyl ether acetates; N-acylamino acids or salts thereof; N-acylmethyl taurine salts; alkyl sulfates, polyoxyalkyl ether sulfates. Salt; Alkyl Sulfate Polyoxyethylene Alkyl Ether Phosphate; Loginate Soap; Himasi Oil Sulfonate Esalt; Lauryl Alcohol Sulfonic Acid Esalt; Alkylphenol Sulfonic Acid Ester; Alkyl Sulfonic Acid Ester; Alkylaryl Sulfonate; Examples thereof include sulfo-aquatic acid systems such as amber acid salt, diethyl hexylsyl sulfo sulphate, and dioctyl sulfo sulphate.
Various types of these surfactants are commercially available. As an example, for example, Lion Co., Ltd., Lipearl 835I, 860K, 870P, NTD, MSC; Adeca Co., Ltd., Adecacol EC8600; Kao Corporation Perex OT-P, CS, TA, TR; Shin Nihon Rika Co., Ltd. Company, Rika Mild ES-100, ES-200, Rika Surf P-10, M-30, M-75, M-300, G-30, G-600; Toho Chemical Industry Co., Ltd., Kohakunor L-300, Examples thereof include L-40, L-400, and NL-400.

Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly4-vinylpyridine derivative.

Examples of amphoteric tensides include betaine lauryldimethylaminoacetic acid, 2-alkyl-N-carboxymethyl-N'-hydroxyethylimidazolinium betaine, betaine coconut oil fatty acid amide propyldimethylaminoacetic acid, polyoctylpolyaminoethylglycine, and imidazoline derivatives. And so on.

Examples of the nonionic surfactant include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Ethers such as polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-Tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3,5-dimethyl-1-hexin-3-ol Etc. acetylene glycol (alcohol) type; Nisshin Kagaku Co., Ltd., Surfinol 104, 104PG50, 105, 82, 465, Orphine STG, etc .; Polyglycol ether type (for example, SIGMA-ALDRICH Co., Ltd. Tergitol 15-S-7, etc.) ) Etc. can be mentioned.

Examples of the silicone-based surfactant include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and the like. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane); BYK-345, BYK-348 (polyether-modified polydimethylsiloxane), all of which are manufactured by Big Chemie.

Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group. Examples thereof include a polyoxyalkylene ether polymer compound contained in. Specific examples thereof include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 manufactured by DuPont; PF-manufactured by Omniova. 151N, PF-154N and the like can be mentioned.

Examples of the defoaming agent include highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, silicone-based, and acetylene glycol-based compounds.

The ink can be used for various recordings. For example, it is suitable for writing tools, water-based printing, information recording, fiber dyeing, inkjet recording and the like.
When the ink is used as an inkjet ink, the viscosity at 25 ° C. is usually 3 mPa · s to 20 mPa · s, preferably 8 mPa · s to 20 mPa · s as measured by an E-type viscometer.
Similarly, the surface tension of the ink at 25 ° C. is usually 20 mN / m to 40 mN / m, preferably 25 mN / m to 35 mN / m when measured by the plate method.
Similarly, the dynamic surface tension of the ink at 5 ° C. at 10 Hz is usually 25 mN / m to 45 mN / m, preferably 30 mN / m to 40 mN / m when measured by the maximum foam pressure method.

The substrate is roughly classified into one having an ink receiving layer and one having no ink receiving layer. Any of these is preferable as the base material used in the inkjet recording method.
Specific base materials include, for example, paper, film, fibers and cloths (polyester, cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like.
The ink receiving layer is installed on the base material for the purpose of absorbing ink and accelerating its drying. The ink receiving layer is provided, for example, by a method of impregnating or coating the base material with a cationic polymer; a method of coating inorganic fine particles together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone on the surface of the base material. Will be done. Examples of the inorganic fine particles include porous silica, alumina sol, and special ceramics.
A substrate having such an ink receiving layer is usually called an inkjet paper, an inkjet film, a glossy paper, a glossy film, or the like. Examples of commercially available inkjet paper include professional photo paper manufactured by Canon Inc.
Further, examples of the paper having no ink receiving layer include plain paper and the like. Examples of commercially available plain paper include plain paper copy (PPC) paper and the like.
The substrate to which the ink containing the dye mixture is attached is included in the scope of the present invention. Examples of such a base material include paper on which characters, symbols, various designs and the like are recorded. Such a base material can be used as it is for appreciation and the like. Further, it can also be used as an intermediate recording medium used for thermal transfer (sublimation transfer) of the above characters or the like to another base material such as fibers.

The ink can record very well on the fibers of the base material. The type of fiber is not particularly limited, but hydrophobic fiber is preferable. Examples of the hydrophobic fiber include polyester fiber, nylon fiber, triacetate fiber, diacetate fiber, polyamide fiber, and blended fiber using two or more kinds of these fibers. In addition, these fibers and regenerated fibers such as rayon; and blended fibers of these fibers and natural fibers such as cotton, silk, and wool are also included in the hydrophobic fibers in the present specification.
Some fibers are known to have an ink receiving layer, and such fibers can also be preferably used. The fiber having an ink receiving layer can be prepared by a known method or can be obtained as a commercial product. The material and structure of the ink receiving layer are not particularly limited, and can be appropriately used depending on the purpose and the like.

The method of adhering the ink to the substrate is not particularly limited, and all known methods (for example, various writing tools, inkjet recording, etc.) can be used. When the fiber is used as the base material, a surface coating dyeing method including a size pressing method, a coating method and the like, an internal dyeing method and the like can also be used. In addition, the above-mentioned dye composition includes those having sublimation property. Such dye compositions can also be preferably used in sublimation transfer dyeing methods.

For all the above-mentioned matters, the combination of preferable ones is more preferable, and the combination of more preferable ones is further preferable. The same applies to a combination of a preferable one and a more preferable one.
Further, all the above-mentioned components including the compound represented by the formula (1) and the colorant A can use a single component thereof. In addition, two or more types can be used in combination as needed.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the functional groups in each formula are expressed in free form.
"Water" in the examples means "ion-exchanged water" unless otherwise specified.
The maximum absorption wavelength (λmax) was measured using a visible ultraviolet spectrophotometer UV2550 manufactured by Shimadzu Corporation. For the test solution, 0.015 g of the compound to be measured is diluted with 250 ml of a 75% acetone aqueous solution (a mixture of 75% acetone and 25% water), and then 1 ml of this diluted solution is further diluted with 25 ml of a 75% acetone aqueous solution. Prepared.

[Example 1]: Synthesis of a compound represented by the following formula (6).
To 75 parts of sulfolane, 3.0 parts of 1,4-diamino-2,3-anthraquinone dicarboxyimide and 25 parts of 3-aminopentane were added to obtain a liquid. The obtained liquid was heated to 140 ° C. in an autoclave and reacted for 6 hours to obtain a liquid. The obtained liquid was cooled to room temperature, and the precipitated solid was separated by filtration. The obtained solid was washed with 100 parts of methanol and 200 parts of water and then dried to obtain 3.1 parts of the compound represented by the following formula (6) (λmax = 664 nm).

[Preparation Example 1]: Preparation of a solution of a dispersant.
John Krill 678 (40 parts) was added to a mixture of 48% aqueous sodium hydroxide solution (3.1 parts), ion-exchanged water (96.9 parts), and propylene glycol (60 parts), and heated to 90 ° C. Stirring for 5 hours gave a solution of dispersant. “JC678” in Table 1 below means a solution of this dispersant.

[Examples 1 to 4 and Comparative Examples 1 to 5]: Preparation of dispersion.
Each component shown in Table 3 below was mixed to obtain a liquid. The obtained liquid was placed in a sand mill, 0.3 mm zirconia beads were added, and a dispersion treatment was performed under water-cooled conditions at 1500 rpm for 15 hours to obtain a liquid. By adding ion-exchanged water to the obtained liquid and diluting it, a liquid having the total content of the colorant adjusted to 15% was obtained. By filtering this liquid with a glass fiber filter paper GC-50 (manufactured by ADVANTEC), dispersion liquids of Examples 1 to 4 and Comparative Examples 1 to 4 having a total colorant content of 15% were obtained, respectively. .. The "total content of the colorant" used here means the total content of the compound represented by the formula (6) and the dispersant A.

The abbreviations and the like in Table 1 below represent the following meanings.
Formula (6): The compound represented by the formula (6) obtained in Example 1.
DB72: C.I. I. Disperse Blue 72 (λmax = 583nm).
DB60: C.I. I. Disperse Blue 60.
DB359: C.I. I. Disperse Blue 359.
SF104: Surfinol 104PG50.
GXL: Proxel GXL.

[Ink preparation]
Using the dispersions obtained in Examples 1 to 4 and Comparative Examples 1 to 4, the liquids obtained by mixing the components shown in Table 4 below are filtered through a 5 μm membrane filter. Inks for evaluation tests of Examples 5 to 8 and Comparative Examples 5 to 8 were obtained. The total content of the colorant contained in each ink was adjusted to 4.8%.

[Preparation of dyed cloth]
The ink obtained as described above was applied to a transfer paper (manufactured by Kiwa Kagaku Co., Ltd.) and dried at 60 ° C. for 30 minutes to obtain transfer papers to which each ink was attached. All of these transfer papers were dyed cyan. Each of the obtained transfer papers is cut into 20 cm x 8 cm, and after superimposing the polyester cloth tropical (manufactured by Teijin Co., Ltd.) of the same size on the dyed surface of the transfer paper, a transfer press machine manufactured by Taiyo Seiki Co., Ltd. A blue dyed cloth was obtained by heat-treating using "TP-600A2" at 200 ° C. for 60 seconds and sublimating transfer from the transfer paper to the polyester cloth.
The dyed cloths dyed with the inks of Examples 5 to 8 are referred to as dyed cloths 1 to 4, respectively. Further, the dyed fabrics dyed with the inks of Comparative Examples 5 to 8 are referred to as comparative dyed fabrics 1 to 4, respectively.

[Measurement of staining concentration]
The reflection density (Dc value) of each dyed cloth and the comparative dyed cloth obtained as described above was measured using a colorimeter manufactured by X-Rite, SpectroEye. The measurement was performed under the conditions of ANSI A, a viewing angle of 2 degrees, and a light source D65 based on the concentration. The higher the Dc value, the darker the stain, and therefore the sublimation transferability is excellent. The measurement results are shown in Table 5 below.

[Hue evaluation]
The hue (L *, C *, h) and optical density (Dc) of each dyed cloth obtained as described above and the comparative dyed cloth were measured using a colorimeter manufactured by X-rite, SpectroEye. .. The measurement was performed under the conditions of ANSI A, a viewing angle of 2 degrees, and a light source D65 based on the concentration. Hue evaluation was evaluated according to the following three-step criteria.
A: h, * C, L falls within the range of 278 <h <298, 60 <* C, 32 <L.
B: Any two items of h, * C, and L fall within the range of 278 <h <298, 60 <* C, 32 <L.
C: Any one of h, * C, and L falls within the range of 278 <h <298, 60 <* C, 32 <L.

[Light resistance test]
The light resistance test was performed according to the JIS L0843A method. That is, under the conditions of black panel temperature 63 ° C, tank temperature 38 ° C, relative humidity 50%, radiation illuminance 50 W / m ² (300 to 400 nm), inner filter quartz, and outer filter soda lime glass, xenon weather meter SUGA NX75 ( Using a Suga Test Instruments Co., Ltd.), each dyed cloth obtained as described above was irradiated with light for 39.4 hours using a light source xenon arc.
Each dyed cloth after this light irradiation was visually judged according to the blue scale grade specified in JIS L-0841, and the light resistance judgment grade was determined. The light resistance grades of the judgment results are shown in Table 3 below.

As is clear from Table 5, it was confirmed that each of the dyed fabrics of the examples had good dyeing density, hue, and light resistance.
On the other hand, each comparative dyed fabric has good light resistance, but the hue is slightly insufficient. In addition, it was clarified that the sublimation transferability was inferior because the staining concentration was low.

The blue dye mixture of the present invention has good light resistance and good sublimation transferability. Therefore, it is extremely useful as a blue dye composition used for dyeing various base materials, preferably fibers, more preferably hydrophobic fibers.

Claims (9)

Colorant A having a chemical structure different from that of the compound represented by the following formula (1) and the compound represented by the following formula (1) and having a maximum absorption wavelength in the range of 550 nm to 700 nm (however, A blue dye composition containing (excluding azo disperse dyes) .

[In the formula (1), R1 is a hydrogen atom, R2 is a C1-C4 alkyl group, R3 is a C1-C4 alkyl group, and the total number of carbon atoms of R2 and R3 is 4 to 8. , X represent an oxygen atom. ] The colorant A is C.I. I. DisperseBlue, C.I. I. DisperseViolet, and C.I. I. The blue dye composition according to claim 1, which is a dye selected from SolventBlue. An ink containing at least one liquid medium selected from water and an organic solvent and the blue dye composition according to claim 1 or 2. The ink according to claim 3, further containing a dispersant. A base material to which the blue dye composition according to claim 1 or 2 is attached. A base material to which the ink according to claim 3 or 4 is attached. The base material according to claim 5 or 6, wherein the base material is a fiber. The base material according to claim 7, wherein the fiber is a hydrophobic fiber. The base material according to claim 8, wherein the hydrophobic fiber is polyester or a blended fiber containing polyester.