JPH06329927A - Ink composition for ink jet printing and dyeing method using the same - Google Patents

Abstract

PURPOSE:To obtain an ink composition for ink jet printing which gives a clear blue printed product excellent in long-term dispersibility and printability and is useful for printing hydrophobic fibers such as polyester by incorporating specific disperse dye (s). CONSTITUTION:The ink composition comprises one or more disperse dyes represented by the formula [wherein R1 is H, Cl, Br, CH3 or OCH3; R2 is H, CH3, OCH3 or OC2H5; and R3 and R4 are each H, a 1-6C alkyl (substituted by Cl, Br, CN, a 1-6C alkoxy, an aryl, an aryloxy, a carbo-(1-6C) alkoxy acetoxy or allyloxy), allyl or a cycloalkyl, or may be combined with each other to form a heterocyclic residue].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disperse dye ink composition for inkjet printing. In particular, the present invention relates to an ink composition for inkjet printing, which is suitable for printing a woven or non-woven fabric made of hydrophobic fibers such as polyester and acetate, or a mixed woven fabric made of these fibers and other fibers.

[0002]

2. Description of the Related Art Conventionally, a so-called ink jet printing method has been known in which ink droplets are ejected from minute ejection orifices for printing. Various types of printing methods have been proposed. The representative ones are as follows. Continuous jet type: An ink droplet is ejected from a minute nozzle by pressurization, the droplet is made to have a constant cycle by vibration, and a droplet whose charge amount is controlled by being charged with a high voltage is generated. Printing is performed by causing droplets to fly between deflection electrodes to which a uniform electric field is applied. On-demand type: For example, an electric signal is applied to a printer head having a piezo element, ink is controlled by pressure according to the signal to generate droplets, and a bubble is generated by applying an electric signal to a heating resistance element. Control the ink with and print.

Such an ink jet printing system is
Ink droplets are ejected and the ink droplets are attached to a material to be dyed for printing. Such an ink contains a coloring material and a liquid medium in which the coloring material is dispersed (water, various organic solvents, or a mixture thereof) as a basic component, and may contain various additives as necessary.

The preferable conditions for this type of ink are:
Does not clog the discharge orifice, has liquid properties suitable for discharge (viscosity, surface tension, conductivity, etc.), does not change physical properties or solids during storage, and has a high concentration To give fast fixing to the material to be dyed, little ink bleeding, excellent water resistance and light resistance, little odor and toxicity, and excellent safety such as flammability, etc. Is mentioned.

Since the ink applied to the print for the purpose is basically composed of the dye and the solvent thereof as described above, the characteristics of the above-mentioned ink are unique to the dye and the component used as the liquid medium. It greatly depends on the nature of.

Further, by adopting the ink jet printing system, the BOD and COD loads of the waste water after dyeing, which has recently become a social requirement from the environmental aspect, can be greatly reduced. This is due to the fact that it is possible to greatly reduce the printing paste by the inkjet printing method, and it is desirable that the ink side itself also has a small drainage load. That is, it is desired that the amount of various additives added is small and the dye has a high concentration and good storage stability over a long period of time.

In order to perform full-color inkjet print dyeing efficiently at low cost, it is necessary to reduce the number of printer heads as much as possible. Actually, three primary colors of yellow, cyan, and magenta are often used, and when black is included, four colors are often used. Further, some other colors may be added and used. The characteristics of the dyes used for these are required to produce a wide range of colors with as few colors as possible. That is, of the spectral absorption characteristics of each color, it is required that the molecular extinction coefficient is high, that is, the color value is high, and the color tone is dull, that is, clear. The high color value is advantageous in that the dye concentration in the ink can be kept relatively low, and the load of dyeing wastewater can be reduced, and also that a wide range of densities can be exhibited. Further, the dye used for printing on the fiber is required to have excellent dyeing properties, for example, dyeing reproducibility, light fastness, various fastnesses such as fastness to sublimation, and white spot stain resistance.

From this viewpoint, ink jet printing inks using disperse dyes have been proposed. For example, one in which a disperse dye is dissolved in an organic solvent (Japanese Patent Publication No. 54-21).
766, JP-A-60-75693), or a type in which a disperse dye is dispersed in water (JP-A-60-
75692, 60-133076, Japanese Patent Publication No. 62-57750, Japanese Patent Laid-Open No. 4-33309, etc.).

However, the dissolution type ink has a low solubility of the disperse dye and it is difficult to produce an ink composition having a high dye concentration, and the dispersion type ink composition is still a problem in terms of dispersion stability. Is not resolved.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink composition for inkjet printing, which is excellent in dispersion stability over a long period of time, is suitable for inkjet printing, and is clear and has excellent dyeing properties. .

[0011]

The present inventors have accomplished the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention provides (1) an ink composition for inkjet printing for hydrophobic fibers containing at least one kind of the disperse dye represented by the formula (1).

[0012]

[Chemical 2]

(In the formula (1), R ₁ represents a hydrogen atom, chlorine atom, bromine atom, methyl group or methoxy group, R ₂ represents a hydrogen atom, methyl group, methoxy group or ethoxy group, and R ₃ , R ₄ is a hydrogen atom, a linear or branched alkyl group, or an optionally substituted alkyl group (provided that the substituent is a chlorine atom, a bromine atom, a cyano group,
An alkoxy group, an aryl group, an aryloxy group, a carboalkoxy group, an acetoxy group and an allyloxy group are shown. ), An allyl group and a cycloalkyl group, respectively, and R ₃ and R ₄ may together form a heterocyclic residue. Here, the alkyl group and the alkoxy group mean those having 1 to 6 carbon atoms. ) (2) The disperse dye represented by the formula (1) is 5 as a dye base.
The ink composition for inkjet printing according to the above item (1), which accounts for 0% by weight or more (3) The ink composition for inkjet printing according to the above item (1), which contains water and a hydrophilic organic solvent (4) The above item (1) A method for dyeing a hydrophobic fiber, which comprises using the ink composition according to any one of (3) to (3).

The disperse dye represented by the formula (1) used in the present invention is known from Japanese Patent Publication No. 61-5501. Disperse dyes of the formula (1) are known to dye hydrophobic fibers, for example polyethylene terephthalate fibers, in a vivid blue.

Specific examples of preferred substituents in the formula (1) are as follows. R ₃ and R ₄ are each a linear or branched substituted alkyl group having 1 to 6 carbon atoms in addition to a hydrogen atom, for example, β-chloroethyl, β-bromoethyl, β-cyanoethyl, β-methoxyethyl, β-ethoxyethyl, β-butoxyethyl, γ-methoxypropyl, γ-methoxybutyl, γ
-Phenylpropyl, β-phenylethyl, benzyl,
β-phenoxyethyl, β-carbomethoxyethyl, β
-Carboethoxyethyl, β-acetoxyethyl or a cycloalkyl group such as cyclopentyl or cyclohexyl, and examples of the nitrogen atom and R ₃ or R _{4 taken} together include a residue of piperidine or morpholine.

The disperse dyes represented by the above formula (1) used in the present invention may be used alone or in admixture of two or more kinds, and further adjusted to a desired hue, and the fastness and dyeing property are improved. Therefore, it is possible to mix and use several kinds of existing disperse dyes. It is possible to mix with other dyes of the three primary colors.
The dye base may be blended in advance and then finely divided, or each dye may be dispersed (fine grained) and then blended to produce an ink composition for inkjet printing. The disperse dye represented by the formula (1) is preferably used in an amount of 50% by weight or more of the dye content. The blending ratio of other dyes optionally blended is not constant depending on the kind of the dye, but the same weight% with respect to the amount of the dye of the formula (1) used.
The following is preferable.

Examples of other dyes that can be blended include known dyes represented by the following formula.

[0018]

[Chemical 3]

(In the formula (2), X is a chlorine atom, a bromine atom,
It means a cyano group or a nitro group, Y means an alkyl group or an acylamino group, and R ₁ and R ₂ are each a hydrogen atom, a linear or branched alkyl group, or an optionally substituted alkyl group (provided that it is a substituent. Is a chlorine atom, a bromine atom, a cyano group, an alkoxy group, an aryl group,
An aryloxy group, a carboalkoxy group, an acetoxy group and an allyloxy group are shown. ), An allyl group, and a cycloalkyl group. Here, the alkyl group and the alkoxy group mean those having 1 to 4 carbon atoms. )

(In the formula (3), R ₁ and R ₂ are each an alkyl group and an optionally substituted phenyl group (provided that the substituent is a chlorine atom, a bromine atom, an alkyl group or an alkoxy group)). Means.)

(In the formula (4), R means an alkyl group, an alkoxyalkyl group or an alkoxyalkoxyalkyl group, and X means O, S or NH. Here, the alkyl group and the alkoxy group have carbon numbers. 1 to 4 are meant.)

(In the formula (5), R ₁ represents a hydrogen atom, an alkyl group, an alkoxyalkyl group or an allyl group, and R 1
₂ and R ₃ are each a linear or branched alkyl group and an optionally substituted alkyl group (provided that the substituent is a chlorine atom, a bromine atom, a hydroxy group, a cyano group, an alkoxy group, an aryl group, an aryloxy group) , Carboalkoxy group, acetoxy group, allyloxy group), allyl group, cycloalkyl group, and R
₂ and R ₃ may together form a heterocyclic residue. Here, the alkyl group and the alkoxy group have 1 carbon atoms.
It shall mean one to four. )

In the ink composition of the present invention, the amount of the dye base material containing at least one of the disperse dyes represented by the above formula (1) is 1 to 30% by weight, preferably 2% by weight based on the total weight of the ink liquid. Is in the range of 20% by weight. A liquid medium containing water and a hydrophilic organic solvent is used as the liquid medium of the ink composition of the present invention. Here, the hydrophilic organic solvent has an effect as a non-drying agent, has a role of preventing the generation of solid matter by drying, and also has a role of adjusting the viscosity of the ink composition.

As the hydrophilic organic solvent, polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, 3-methylpentane-1,3,5-triol, propylene glycol,
One or more of alkylene glycols such as butylene glycol; glycerin; nitrogen-containing heterocyclic ketones such as N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone can be used as the liquid medium component.

The content of the hydrophilic organic solvent in the ink composition is generally 1 to 50% by weight, preferably 4 to 30% by weight based on the total weight of the ink liquid.

In the ink composition of the present invention, it is preferable to use a dye finely divided with an anionic or nonionic surfactant. Examples of anionic surfactants that can be used for making fine particles of dyes include lignin sulfonates, formalin condensates of naphthalene sulfonates, formalin condensates of alkylnaphthalene sulfonates, and formalin of special aromatic sulfonates. Examples thereof include a condensate and a formalin condensate of creosote oil sulfonate. Examples of nonionic surfactants that can be used include block copolymers of ethylene oxide and propylene oxide, and ethylene oxide adducts of alkylphenols.

The above-mentioned surfactants can be used alone or in a mixture. The amount used is usually in the range of 0.2 to 5 times, preferably 0.5 to 2 times the weight ratio of the bulk powder.

In preparing the ink composition of the present invention, one or a mixture of the above-mentioned surfactants and water are added to the dye raw material represented by the above formula (1) and a ball mill or a sand mill is used. Sufficiently wet pulverize to make the average particle size of the dye 3 μm or less, preferably 0.1 μm or less, add a nonionic or anionic surfactant if necessary, and use water and a hydrophilic organic solvent to obtain a desired amount. After diluting to a dye concentration, dyes, dusts, foreign substances and the like having large particle diameters are removed by passing them through a filter as needed and then used. When a nonionic or anionic surfactant is used, it is contained in the ink composition in an amount of 0.05 to 20% by weight, preferably 0.1 to 10% by weight. In order to dye hydrophobic fibers, for example, a polyethylene terephthalate woven fabric, using the ink composition for inkjet printing of the present invention, the woven fabric is printed with an on-demand type ink jet printer and dried at 60 ° C. to 100 ° C. Is maintained at 100 ° C. to 200 ° C., preferably 150 ° C. to 180 ° C. for usually 1 minute to 20 minutes, preferably 5 minutes to 10 minutes for color development (high temperature atmospheric pressure steaming fixing method), The target dyed product can be obtained by performing reduction washing. It is also possible to pretreat a woven fabric to be dyed with a water-soluble polymer or the like in advance in order to quickly absorb and retain the ink composition of the present invention.

The ink composition for inkjet printing of the present invention thus prepared has not only a vivid color tone and a wide range of coloration but also excellent stability among various characteristics and long-term storage. Has no sedimentation,
Moreover, it is also characterized in that the discharge orifice is not clogged. When a bactericidal or antifungal agent (for example, Deltop manufactured by Takeda Pharmaceutical Co., Ltd.) is added, it may be added before the filtration.

[0030]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples,% and parts are based on weight.

Example 1 The following formula (6) obtained by synthesis by a known method

[0032]

[Chemical 4]

10 parts of disperse dye raw material represented by: and formalin condensate of sodium methylnaphthalene sulfonate 15
Parts and 50 parts of water were wet pulverized in the presence of 100 parts by volume of glass beads in a sand mill for 48 hours to form fine particles. The glass beads were removed by filtration to obtain 70 parts of a dispersion liquid. To this, 2 parts of a block copolymer of ethylene oxide and propylene oxide and 55 parts of glycerin and 60 parts of water were added to obtain an ink composition having a dye concentration of 5%. This is further passed through a 10-micron filter to remove those with large dye particles and foreign substances, and an average particle diameter of 0.0 for inkjet printing.
A 6% 5% ink composition was obtained. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained according to the above examples,
After printing on polyethylene terephthalate fiber with an on-demand type inkjet printer and drying at 80 degrees,
It was kept in 170 ° C. superheated steam for 7 minutes, washed with water, reduced, washed with water, and dried. A dyed product in which the printed portion was colored in a vivid blue color was obtained. This was a beautiful dyeing without bleeding. In order to show that the dye represented by the formula (1) is extremely excellent as the blue component for the ink jet print 3 primary colors in terms of brightness and color intensity (color variation), it was absorbed by a Hitachi U-3210 type self-recording spectrophotometer. When the spectrum was measured, it was as shown in FIG. 1A, and the half-width (Δλmax1 / 2) was calculated to be 92 nm. The C.I. I. It shows that the dye of the formula (1) is a very clear pigment because it shows a small value with respect to the full width at half maximum of Disperse Blue 60 (calculated from FIG. 1 (B)). Further, the extinction coefficient (ε) is 55680 as calculated from FIG. 1, which is a very large value as compared with the dye ε of the comparative example being 14000, which indicates that the color intensity is extremely high. Further, the dyed product obtained in Example 1 and the dyed product of the dye of the comparative example are Macbeth CE-3.
000 and measure CIE chromaticity diagram L * (Elster), a
The values of * (Aster), b * (Bee star) and c * (Sea star) were determined. Here, L * is the lightness, a * b
* Is a unit of formula degree representing hue and saturation, and c * is a unit representing saturation. The result is L * = 50.78, a * =
-5.11, b * =-49.82 and c * = 50.0
It was 8. C. shown in the following comparative example. I. Since it shows a very large value with respect to the value of Desperse Blue 60, it can be seen that the dyed cloth obtained in Example 1 has an extremely clear color tone.

Comparative Example 1 C. I. The spectral absorption spectrum of Disperse Blue 60 was measured in the same manner as in Example 1, and FIG.
And the half-width was calculated to be 112 nm. Further, a dyed product was obtained using this dye in the same manner as in Example 1, and the color was measured with Macbeth CE-3000 to obtain L of the CIE chromaticity diagram.
The values of *, a *, b * and c * were obtained. L * = 56.5
4, a * = − 17.07, b * = − 34.55 and c * = 38.54.

Example 2 The following formula (7) obtained by synthesis in the same manner as in Example 1

[0037]

[Chemical 5]

15 parts of the disperse dye raw material represented by, 15 parts of formalin condensate of sodium naphthalenesulfonate, 5 parts of sodium ligninsulfonate and 50 parts of water were wet-milled for 36 hours in a sand mill in the presence of 100 parts by volume of glass beads. It was made into fine particles. The glass beads were removed by filtration to obtain 85 parts of a dispersion liquid. To this, 1 part of a block copolymer of ethylene oxide and propylene oxide, 40 parts of glycerin and 33 parts of ion-exchanged water were added, and the average particle size was 0.0
An 8% 8% ink composition was obtained. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained according to the above examples,
After printing on polyethylene terephthalate fiber with an on-demand type inkjet printer and drying at 80 degrees,
It was kept in 170 ° C. superheated steam for 7 minutes, washed with water, reduced, washed with water, and dried. A dyed product in which the printed portion was colored in a vivid blue color was obtained. This was a beautiful dyeing without bleeding.

Example 3 The above formula (6) and the following formula (8) obtained by synthesis by a known method.

[0041]

[Chemical 6]

Disperse dye base 1 of a 3: 1 mixture represented by
5 parts, 17 parts formalin condensate of sodium naphthalene sulfonate, 5 parts sodium lignin sulfonate and 6 parts water
3 parts were wet pulverized with a sand mill for 48 hours in the presence of 100 parts by volume of glass beads to form fine particles. The glass beads were removed by filtration to obtain 95 parts of a dispersion liquid. In addition to this, 1 part of a block copolymer of ethylene oxide and propylene oxide, 48 parts of ethylene glycol and 46 parts of ion-exchanged water.
7.5 parts of an ink composition having an average particle diameter of 0.1 micron was obtained. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained according to the above examples,
The same operation as in Example 1 was performed (that is, the polyethylene terephthalate fiber was subjected to printing, drying, superheated steam treatment, washing with water, reducing washing, washing with water, and drying with an on-demand type ink jet printer). A dyed product in which a portion was colored in a clear blue color was obtained. This was a beautiful dyeing without bleeding. The light fastness and fastness to sublimation of this dyed product were further improved as compared with the dyed product obtained in Example 1.

Example 4 The above formula (6) obtained by synthesis by a known method and the following formula (9)

[0045]

[Chemical 7]

Disperse dye stock 1 of a 3: 1 mixture of
2 parts, formalin condensate of sodium naphthalene sulfonate 15 parts, sodium lignin sulfonate 5 parts and water 6
8 parts were wet pulverized for 48 hours in the presence of 100 parts by volume of glass beads in a sand mill to form fine particles. The glass beads were removed by filtration to obtain 90 parts of a dispersion liquid. To this, 2 parts of an ethylene oxide 85 mol adduct of nonylphenol, 50 parts of ethylene glycol and 74 parts of ion-exchanged water were added to obtain a 5% ink composition having an average particle size of 0.1 micron. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained according to the above examples,
The same operation as in Example 1 was performed (that is, the polyethylene terephthalate fiber was subjected to printing, drying, superheated steam treatment, washing with water, reducing washing, washing with water, and drying with an on-demand type ink jet printer). A dyed product in which a portion was colored in a clear blue color was obtained. This was a beautiful dyeing without bleeding. The fastness to light of this dyed product was further superior to that of the dyed product obtained in Example 1.

Example 5 The above formula (6) and the following formula (10) obtained by synthesis by a known method.

[0049]

[Chemical 8]

Disperse dye base 1 of a 3: 1 mixture represented by
8 parts, 10 parts formalin condensate of sodium naphthalene sulfonate, 6 parts sodium lignin sulfonate and 6 parts water
6 parts were wet-ground for 40 hours in a sand mill in the presence of 100 parts by volume of glass beads to form fine particles. The glass beads were removed by filtration to obtain 90 parts of a dispersion liquid. 0.5 parts of a block copolymer of ethylene oxide and propylene oxide, 20 parts of ethylene glycol and 24.5 parts of ion-exchanged water were added thereto to obtain a 12% ink composition having an average particle size of 0.1 micron. The ink composition for inkjet printing obtained in this example has a room temperature or a low temperature (0 degree Celsius).
In addition, it showed good stability without aggregation or precipitation for more than 1 month.

Using the inks obtained in the above examples,
The same operation as in Example 1 was performed (that is, the polyethylene terephthalate fiber was subjected to printing, drying, superheated steam treatment, washing with water, reducing washing, washing with water, and drying with an on-demand type ink jet printer). A dyed product in which a portion was colored in a clear blue color was obtained. This was a beautiful dyeing without bleeding. The light fastness and fastness to sublimation of this dyed product were further improved as compared with the dyed product obtained in Example 1.

Example 6 The above formula (6) obtained by synthesizing by a known method and the following formula (1)
1) and formula (12)

[0053]

[Chemical 9]

In the presence of 100 parts by volume of glass beads, 18 parts of a 3: 1: 1 mixture of a disperse dye base, 18 parts of a sodium formalin sulfonate formalin condensate, 4 parts of sodium lignin sulfonate and 60 parts of water were added. Wet grinding was carried out for 48 hours with a sand mill to make fine particles. The glass beads were removed by filtration to obtain 90 parts of a dispersion liquid. 0.5 parts of a block copolymer of ethylene oxide and propylene oxide, 40 parts of glycerin and 3 parts of ion-exchanged water.
1.5 parts was added to obtain an ink composition having an average particle size of 0.1 micron and 10%. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained according to the above examples,
The same operation as in Example 1 was performed (that is, the polyethylene terephthalate fiber was subjected to printing, drying, superheated steam treatment, washing with water, reducing washing, washing with water, and drying with an on-demand type ink jet printer). A dyed product in which a portion was colored in a clear blue color was obtained. This was a beautiful dyeing without bleeding.

Example 7 The above formula (6) obtained by a known method and the following formula (13),
(14)

[0057]

[Chemical 10]

In the presence of 100 parts by volume of glass beads, 15 parts of a 4: 1: 1 mixture of a disperse dye base, 15 parts of a sodium formalin sulfonate formalin condensate, 6 parts of sodium lignin sulfonate and 64 parts of water are used. Wet grinding was carried out for 52 hours with a sand mill to make fine particles. The glass beads were removed by filtration to obtain 90 parts of a dispersion liquid. To this was added 3 parts of a block copolymer of ethylene oxide and propylene oxide, 48 parts of ethylene glycol and 99 parts of ion-exchanged water to obtain a 6% ink composition having an average particle size of 0.09 micron. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained according to the above examples,
The same operation as in Example 1 was performed (that is, the polyethylene terephthalate fiber was subjected to printing, drying, superheated steam treatment, washing with water, reducing washing, washing with water, and drying with an on-demand type ink jet printer). A dyed product in which a portion was colored in a clear blue color was obtained. This was a beautiful dyeing without bleeding. The light fastness and sublimation fastness of this dyed product were further superior to those of the dyed product obtained in Example 1.

Example 8 The above formula (6) obtained by synthesis by a known method and the following formula (1)
5)

[0061]

[Chemical 11]

Disperse dye base 1 of a 5: 1 mixture of
8 parts, 14 parts of formalin condensate of sodium methylnaphthalene sulfonate, 4 parts of sodium lignin sulfonate and 64 parts of water were wet pulverized in a sand mill for 48 hours in the presence of 100 parts by volume of glass beads to form fine particles. The glass beads were removed by filtration to obtain 90 parts of a dispersion liquid. To this was added 1 part of a block copolymer of ethylene oxide and propylene oxide, 60 parts of glycerin and 29 parts of deionized water to obtain a 9% ink composition having an average particle size of 0.08 micron. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained according to the above examples,
The same operation as in Example 1 was performed (that is, the polyethylene terephthalate fiber was subjected to printing, drying, superheated steam treatment, washing with water, reducing washing, washing with water, and drying with an on-demand type ink jet printer). A dyed product in which a portion was colored in a bright blue color was obtained. This was a beautiful dyeing without bleeding.

Example 9 15 parts by weight of a 1: 5: 2 mixture of disperse dyes represented by the above formulas (6), (9) and (11) obtained by synthesis by a known method, creosote oil sulfonic acid 22 parts of sodium formalin condensate and 63 parts of water were wet-milled in a sand mill for 50 hours in the presence of 100 parts by volume of glass beads to form fine particles. The glass beads were removed by filtration to obtain 95 parts of a dispersion liquid. To this, 1 part of a block copolymer of ethylene oxide and propylene oxide, ethylene glycol 45
And 37 parts of deionized water were added to obtain an ink composition having an average particle size of 0.09 micron 8%. The ink composition for inkjet printing obtained in this example showed good stability without aggregation or precipitation for one month or longer even at room temperature or low temperature (0 degree Celsius).

Using the inks obtained in the above examples,
After printing on polyethylene terephthalate fiber with an on-demand type inkjet printer and drying at 80 degrees,
It was kept in 170 ° C. superheated steam for 7 minutes, washed with water, reduced, washed with water, and dried. A dyed product in which the printed portion was colored in a vivid blue color was obtained. This was a beautiful dyeing without bleeding. The light fastness and fastness to sublimation of this dyed product were far superior to those of the dyed product obtained in Example 1.

Examples 10 to 30 The following formula (16) was obtained by a known method.

[0067]

[Chemical 12]

A compound represented by the following formula, in which R ₁ , R ₂ , R ₃ and R ₄ have the structures shown in the following table, was synthesized and an ink composition was prepared in the same manner as in Example 1 to prepare these inks. With an on-demand inkjet printer,
It was possible to obtain a dyed product which was printed on a polyester fiber and had a bright blue color without bleeding.

Example R ₁ R ₂ R ₃ R ₄ 10 H CH ₃ C ₂ H ₅ C ₂ H ₅ 11 〃 〃 〃 C ₆ H ₁₃ 12 〃 CH ₂ CH = CH ₂ CH ₂ CH = CH ₂ 13 〃 〃 C ₃ H ₆ Ph C ₂ H ₅ 14 〃 〃 C ₃ H ₆ OCH ₃ C ₃ H ₆ OCH ₃ 15 〃 〃 C ₂ H ₄ CN C ₂ H ₅ 16 〃 〃 〃 C ₂ H ₄ OH 17 〃 〃 C ₂ H ₄ Cl C ₂ H ₄ Cl 18 〃 〃 C ₂ H ₄ Ph C ₄ H ₉ 19 〃 〃 C ₂ H ₄ OCO ₂ CH ₃ C ₂ H ₄ OCO ₂ CH ₃ 20 〃 〃 C ₂ H ₄ OCOCH ₃ C ₂ H ₄ OCOCH ₃ 21 〃 C ₆ H ₁₃ C ₆ H ₁₃ 22 〃 〃 C ₆ H ₁₁ (cyclohexyl group) H 23 〃 〃 morpholine ring 24 〃 〃 piperidine ring 25 6 Br 〃 C ₂ H ₅ C ₂ H ₅ 26 5 over Cl 〃 _{C 4 H 9 C 4 H 9} 27 5 over CH ₃ 〃 _{C 6 H 13 C 6 H 13} 28 5-OCH 3 undefined undefined 29 H 〃 _{C 2 H 5 C 2 H 4} Ph 30 undefined undefined _{C 6 H 13 C 6 H 13} ( where, Ph denotes a phenyl group.)

[0070]

EFFECT OF THE INVENTION A useful ink composition having excellent dispersion stability even after being stored for a long period of time, excellent in ink jet printing suitability for hydrophobic fibers, and giving a clear blue print is obtained.

[Brief description of drawings]

FIG. 1 is an absorption intensity curve of a dye. FIG. 1 (A); Absorption intensity curve of the dye used in Example 1.

FIG. 2 is an absorption intensity curve of a dye. FIG. 1 (B); absorption intensity curve of the dye shown in Comparative Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 11/02 PTF D06P 5/00 111 A 9356-4H

Claims (4)

[Claims] 1. An ink composition for ink-jet printing for hydrophobic fibers containing at least one kind of disperse dye represented by the formula (1). (In the formula (1), R ₁ is a hydrogen atom, a chlorine atom, a bromine atom,
A methyl group or a methoxy group, R ₂ is a hydrogen atom, a methyl group, a methoxy group or an ethoxy group, and R ₃ and R ₄ are a hydrogen atom, a linear or branched alkyl group, or an optionally substituted alkyl group ( However, the substituent includes a chlorine atom, a bromine atom, a cyano group, an alkoxy group, an aryl group, an aryloxy group, a carboalkoxy group, an acetoxy group and an allyloxy group.), An allyl group and a cycloalkyl group, respectively, and R ₃ and R ₄ may together form a heterocyclic residue. Here, the alkyl group and the alkoxy group mean those having 1 to 6 carbon atoms. ) 2. The ink composition for inkjet printing according to claim 1, wherein the disperse dye represented by the formula (1) accounts for 50% by weight or more of the dye base. 3. A water-soluble organic solvent containing water and a hydrophilic organic solvent.
Ink composition for inkjet printing described 4. A method for dyeing a hydrophobic fiber, which comprises using the ink composition according to any one of claims 1 to 3.