JPH073179A - Ink composition for ink jet printing and dyeing method using the same - Google Patents

Abstract

PURPOSE:To obtain the compsn. improved in dispersion stability by dispersing at least one kind of a disperse dye represented by a specific formula in water and a hydrophilic org. solvent. CONSTITUTION:At least one kind of disperse dye represented by formula I (wherein R1 and R2 are each H, alkyl, aryl, etc.; R3 and R4 are each H, Cl, Br, 1-4C alkyl, etc.; and X is NH, O, or NHCO) or a dye mixture comprising 50wt.% or greater the above-mentioned disperse dye and a dye represented by formula II [wherein A is a group of formula III (wherein R is 1-4C alkyl or 1-4C alkoxy), etc.; and X is H, 1-6C alkyl, or 1-6C alkoxy] is mixed and ground in wet with an anionic or nonionic surfactant in an amt. of 0.2-5 times that of the dye or dye mixture and a specified amt. of water on a ball mill, providing a dye dispersion. To the dispersion is added a hydrophilic org. solvent such as polyethylene glycol or glycerin to give an ink compsn. which contains 1-30wt.% dye, has a high dispersion stability during storage, and is used for ink jet printing of a hydrophobic fiber.

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 ink jet printing and a method for dyeing hydrophobic fibers using the same. Especially polyester,
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 acetate or a mixed spun 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 further contains 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, four primary colors of complementary 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 for 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 and R ₂ are each 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 ₁ and R ₂ may together form a heterocyclic residue. R ₃ is a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an alkoxy group,
Means NH, O or CONH. Here, the alkyl group and the alkoxy group mean those having 1 to 4 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 above formula (1) used in the present invention is known from JP-B-42-23606. Disperse dyes of the formula (1) are known to dye hydrophobic fibers, for example polyethylene terephthalate fibers, in bright yellow.

Specific examples of preferred substituents in the formula (1) of the present invention are as follows. R ₁ and R ₂ are each a linear or branched substituted alkyl group having 1 to 4 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-carbethoxyethyl, β-acetoxyethyl or cycloalkyl groups such as cyclopentyl,
Examples thereof include cyclohexyl, and examples of the nitrogen atom together with R ₃ and R ₄ include a residue of piperidine and morpholine.

The disperse dye represented by the above formula (1) used in the present invention is used alone or in a mixture, and further, existing dispersants are used for adjusting a desired hue and improving fastness and dyeing property. It is also possible to mix and use several kinds of 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 the other dye, which is blended if desired, is not constant depending on the kind of the dye, but is preferably the same weight% or less with respect to the amount of the dye of the formula (1) used.

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

[0018]

[Chemical 3]

(In the formula (2), A represents a residue having no water-soluble group, and X represents a hydrogen atom, an alkyl group, an alkoxy group or an alkoxyalkyl group. Here, the alkyl group and the alkoxy group. Means one having 1 to 6 carbon atoms.)

[0020]

[Chemical 4]

(In the formula (3), R means an alkyl group, a tetrahydrofurfuryl group, an alkoxyalkyl group or an alkoxyalkoxyalkyl group. Here, the alkyl group and the alkoxy group have 1 to 4 carbon atoms. Shall mean something.)

(In the formula (4), R means an alkyl group or a phenyl group. Here, the alkyl group and the alkoxy group mean those having 1 to 4 carbon atoms.)

[0023]

[Chemical 5]

(In the formula (5), R has 1 to 4 carbon atoms.
Means an alkyl group or a phenyl group. )

(In the formula (6), R is a linear or branched alkyl group or an optionally substituted alkyl group (provided that the substituent is a hydroxy group or an alkoxy group), and X is an alkoxy group. (Here, the alkyl group and the alkoxy group mean those having 1 to 4 carbon atoms.)

(In the formula (7), R is a hydrogen atom, a chlorine atom,
It means a bromine atom, an alkyl group or an alkoxy group. Here, the alkyl group and the alkoxy group mean those having 1 to 4 carbon atoms. )

(In the formula (8), R means an alkyl group or an alkoxy group. Here, the alkyl group and the alkoxy group mean those having 1 to 4 carbon atoms.)

(In the formula (9), R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an alkoxy group, respectively. It means one having 1 to 4 carbon atoms.)

(In the formula (10), X means a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.)

(In the formula (11), X means a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.)

In the ink composition of the present invention, the content of the dye base material containing at least one kind of the disperse dye represented by the 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 up to 20% by weight. Further, it is preferable to use water and a hydrophilic organic solvent 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 solvent, polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, alkylene glycols such as 3-methylpentane-1,3,5-triol, propylene glycol and butylene glycol; glycerin; N-methyl-2 One or more nitrogen-containing heterocyclic ketones such as -pyrrolidone and 1,3-dimethyl-2-imidazolidinone can be used as a 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 guanine sulfonates, formalin condensates of naphthalene sulfonates, formalin condensates of alkylnaphthalene sulfonates, and formalin condensation of special aromatic sulfonates. And formalin condensates of creosote oil sulfonates and the like. 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 surfactants and water are added to the dye base material represented by the above formula (1), and the mixture is thoroughly mixed with a ball mill or a sand mill. Wet milling to make the average particle size of the dye 3 microns or less, preferably 0.1 microns or less,
If necessary, add a nonionic or anionic surfactant, dilute to the desired dye concentration with water and a hydrophilic organic solvent, and then pass dye, dust, foreign matter, etc. with a large particle size through a filter as necessary. It is then removed before use. 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.

The ink composition for ink jet printing of the present invention thus prepared is characterized in that not only a clear color tone and a wide range of colors can be obtained, but also 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.

To dye hydrophobic fibers such as polyethylene terephthalate white cloth with the ink composition for ink jet printing of the present invention, for example, printing is performed on a woven cloth with an on-demand type ink jet printer and dried at 60 ° C. to 100 ° C. After that, usually 100 ℃ ~ 200
1 minute to 2 at ℃, preferably 160 ℃ to 180 ℃
The desired dyed product can be obtained by holding for 0 minute, preferably 5 to 10 minutes to develop a color (high temperature atmospheric pressure steaming fixing method) and then reducing and washing. It is also possible to pretreat the woven fabric to be dyed with a water-soluble polymer or the like in order to quickly absorb and retain the ink composition of the present invention.

[0039]

EXAMPLES The present invention will be specifically described with reference to examples.
The invention is not limited to only these examples. In the examples,% and parts are based on weight.

Example 1 The following formula (12) obtained by synthesis by a known method

[0041]

[Chemical 6]

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 was added 2 parts of a block copolymer of ethylene oxide and propylene oxide, 55 parts of glycerin and 60 parts of water to obtain an ink composition having a dye concentration of 5%. This is further passed through a 10 micron filter to obtain large dye particles,
A 5% ink composition having an average particle diameter of 0.08 micron for inkjet printing was obtained by removing foreign matters and the like. The ink composition for inkjet printing obtained in this example is
It showed good stability at room temperature and low temperature (0 ° C) without aggregation or precipitation for more than 1 month.

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 clear yellow 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 in the brightness and color intensity (color value) as a yellow component for the ink jet print 3 primary colors, it is spectrally analyzed by a Hitachi U-3210 type self-recording spectrophotometer. When the absorption spectrum was measured, it was as shown in FIG. 1A, and the half-value width (Δλmax1 / 2) was 68 nm when calculated. This is because 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 Yellow 42 (calculated from FIG. 1B). Further, the molecular extinction coefficient (ε) is 47,000 as calculated from FIG. 1, which is a very large value compared to the dye ε of the comparative example of 10400, which indicates that the color intensity is extremely high. Further, the dyed product obtained in Example 1 and the dyed product of the comparative example were subjected to color measurement with Macbeth CE-3000, and L * (Elster), a * (Aster), b * (Beaster) in the CIE chromaticity diagram. ), C * (sea star). Here, L * is lightness, a * b * is a unit of chromaticity that represents hue and saturation, and c * is a unit that represents saturation. The result is L * = 9
9.7, a * =-41.5, b * = 101.2, c *
= 109.2. C. shown in the following comparative example. I. Since the dyed fabric obtained in Example 1 has a very large value with respect to the value of Disperse 42, it can be seen that the dyed fabric has an extremely sharp color tone.

Comparative Example 1 C. I. Example 1 for Disperse Yellow 42
The spectral absorption spectrum was measured in the same manner as in Fig. 1
As shown in (B), the half-width was calculated to be 86 nm. 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 determine the values of L *, a *, b * and c * in the CIE chromaticity diagram. L * = 8
2.2, a * =-40.3, b * = 81.7, c *
= 81.7.

Example 2 The following formula (13) obtained by synthesis in the same manner as in Example 1

[0046]

[Chemical 7]

18 parts of the disperse dye raw material represented by, 18 parts of formalin condensate of sodium naphthalenesulfonate, 6 parts of sodium ligninsulfonate and 58 parts of water are wet-milled for 50 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 90 parts of a dispersion liquid. To this, 1 part of a block copolymer of ethylene oxide and propylene oxide, 31 parts of glycerin and 40 parts of ion-exchanged water were added, and the average particle size was 0.0
An 8 micron 10% ink composition was obtained. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 clear yellow color was obtained. This was a beautiful dyeing without bleeding.

Example 3 The following formula (14) obtained by synthesis by a known method

[0050]

[Chemical 8]

12 parts of the disperse dye raw material shown in, 20 parts of formalin condensate of sodium naphthalenesulfonate, 5 parts of sodium ligninsulfonate and 63 parts of water are wet-milled for 52 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 92 parts of a dispersion liquid. To this was added 1.2 parts of a block copolymer of ethylene oxide and propylene oxide, 27 parts of ethylene glycol and 27 parts of ion-exchanged water to obtain a 7.5% ink composition having an average particle size of 0.07 micron. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 yellow color was obtained. This was a beautiful dyeing without bleeding.

Example 4 The above formula (12) obtained by synthesis by a known method and the following formula (15)

[0054]

[Chemical 9]

Disperse dye stock 1 of a 3: 1 mixture of
0 parts, 16 parts formalin condensate of sodium naphthalenesulfonate, 4 parts sodium ligninsulfonate and 7 parts water
0 part was wet pulverized for 48 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. To this was added 2 parts of an 85 mol adduct of nonylphenyl ethylene oxide, 50 parts of ethylene glycol and 38 parts of deionized water 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 at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 yellow color was obtained. This was a beautiful dyeing without bleeding. The light fastness and fastness to sublimation of this dyed product were higher than those of the dyed product obtained in Example 1.

Example 5 The above formula (12) obtained by synthesizing by a known method, the following formulas (16) and (17)

[0058]

[Chemical 10]

In the presence of 100 parts by volume of glass beads, 20 parts of a 4: 1: 1 mixture of a disperse dye base, 10 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 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. To this, 0.5 parts of a block copolymer of ethylene oxide and propylene oxide, 45 parts of ethylene glycol and 14.5 parts of ion-exchanged water were added, and an average particle diameter of 12 was obtained.
% Ink composition was obtained. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 yellow color was obtained. This was a beautiful dyeing without bleeding. The light fastness of this dyed product was superior to that of the dyed product obtained in Example 1.

Example 6 The above formula (12) and the following formula (18) obtained by synthesis by a known method.

[0062]

[Chemical 11]

Disperse dye stock 1 of a 3: 1 mixture of
7 parts, 17 parts of formalin condensate of sodium naphthalene sulfonate, 6 parts of sodium lignin sulfonate and 6 parts of water
0 part was wet pulverized for 48 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. To this, 1 part of a block copolymer of ethylene oxide and propylene oxide, 40 parts of glycerin and 22 parts of deionized water were added to obtain an ink composition having an average particle size of 0.09 micron 10%. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 having a bright orange color in the part was obtained. This was a beautiful dyeing without bleeding.

Example 7 The above formula (12) obtained by a known method and the following formula (19)

[0066]

[Chemical 12]

Disperse dye stock 1 of 5: 1 mixture represented by
5 parts, formalin condensate of sodium naphthalene sulfonate 15 parts, sodium lignin sulfonate 5 parts and water 6
5 parts 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 90 parts of a dispersion liquid. To this was added 1.8 parts of a block copolymer of ethylene oxide and propylene oxide, 27 parts of ethylene glycol and 50 parts of deionized water to obtain an 8% ink composition having an average particle size of 0.05 micron. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 yellow color was obtained. This was a beautiful dyeing without bleeding. The light fastness and fastness to sublimation of this dyed product were superior to those of the dyed product obtained in Example 1.

Example 8 The above formula (12) obtained by synthesizing by a known method and the following formula (20)

[0070]

[Chemical 13]

Disperse dye stock 1 of 5: 2 mixture represented by
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, 63 parts of glycerin and 26 parts of ion-exchanged 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 at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 part was colored bright yellow was obtained. This was a beautiful dyeing without bleeding. Buildup of this dyed product,
The light fastness and fastness to sublimation were better than those of the dyed product obtained in Example 1.

Example 9 The above formula (12) obtained by synthesis by a known method and the following formula (21)

[0074]

[Chemical 14]

Disperse dye base 1 of a 5: 1 mixture of
8 parts, 14 parts of formalin condensate of sodium naphthalene sulfonate, 4 parts of sodium lignin sulfonate and 6 parts of water
Sand mill 4 in the presence of 100 parts by volume of glass beads 4 parts
It was pulverized by wet pulverization for 2 hours. The glass beads were removed by filtration to obtain 95 parts of a dispersion liquid. 72 parts of ethylene glycol and 61 parts of ion-exchanged water were added thereto to obtain a 7.5% ink composition having an average particle size of 0.08 micron. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 bright orange was obtained. This was a beautiful dyeing without bleeding. The light fastness and fastness to sublimation of this dyed product were extremely superior to those of the dyed product obtained in Example 1.

Example 10 The above formula (12) obtained by synthesizing by a known method and the following formula (22)

[0078]

[Chemical 15]

Disperse dye base 2 of 5: 2 mixture represented by
0 part, 16 parts formalin condensate of sodium naphthalene sulfonate, 4 parts sodium lignin sulfonate and 6 parts water
Sand mill 5 in the presence of 100 parts by volume of glass beads
It was pulverized by wet pulverization for 2 hours. The glass beads were removed by filtration to obtain 90 parts of a dispersion liquid. In addition to this, a block copolymer 2 of ethylene oxide and propylene oxide
Parts, 58 parts of ethylene glycol and 90 parts of ion-exchanged water were added to obtain a 7.5% ink composition having an average particle size of 0.08 micron. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 bright orange was obtained. This was a beautiful dyeing without bleeding. The light fastness and fastness to sublimation of this dyed product were higher than those of the dyed product obtained in Example 1.

Example 11 The above formula (12) obtained by synthesizing by a known method and the following formula (23)

[0082]

[Chemical 16]

Disperse dye base 1 of a 3: 1 mixture of
6 parts, formalin condensate of sodium naphthalene sulfonate 16 parts, sodium lignin sulfonate 4 parts and water 6
Sand mill 5 in the presence of 100 parts by volume of glass beads
It was pulverized by wet pulverization for 2 hours. The glass beads were removed by filtration to obtain 85 parts of a dispersion liquid. In addition to this, a block copolymer 2 of ethylene oxide and propylene oxide
Parts, glycerin 27 parts, ethylene glycol 48 parts and ion-exchanged water 100 parts were added to obtain an 8% ink composition having an average particle size of 0.08 micron. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

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 bright orange was obtained. This was a beautiful dyeing without bleeding.

Example 12 Formulas (12) and (15) obtained by synthesis by a known method
And 15 parts of a 1: 5: 2 mixture of disperse dyes represented by the formula (21), 22 parts of a formalin condensate of creosote oil sodium sulfonate and 63 parts of water, and 100 parts of glass beads 100.
Wet grinding was carried out for 50 hours in a sand mill in the presence of a capacity part to form fine particles. Glass beads are removed by filtration and dispersion 95
I got a part. To this, 1 part of a block copolymer of ethylene oxide and propylene oxide, 45 parts of ethylene glycol and 37 parts of ion-exchanged water were added, and the average particle size was 0.09.
An ink composition of 8% micron was obtained. The ink composition for inkjet printing obtained in this example showed good stability at room temperature and low temperature (0 degree Celsius) without aggregation or precipitation for one month or longer.

Using the inks obtained according to the above examples,
The same operation as in the above example was carried out to obtain a dyed product in which the printed portion was colored in bright yellow. This was a beautiful dyeing without bleeding. Further, the build-up property, light resistance and fastness to sublimation of this dyed product were improved as compared with the dyed product obtained in Example 1.

Examples 12 to 50 The following formula (24) is obtained by a known method.

[0088]

[Chemical 17]

Represented by R ₁ , R ₂ , R ₃ , R ₄ and X
Synthesizes a compound having the structure shown in the following table,
An ink composition was prepared in the same manner as in Example 1, and these inks were used to print on polyester fibers with an on-demand type ink jet printer to obtain a dyed product having a bright yellow color without bleeding.

Example R ₁ R ₂ R ₃ R ₄ X 13 C ₂ H ₅ C ₂ H ₅ 3-CH ₃ H NH 14 〃 〃 3-Cl 〃 〃 15 〃 〃 4-Cl 〃 16 CH ₂ CH = CH ₂ CH ₂ CH = CH ₂ H H 〃 17 C ₂ H ₄ Ph C ₄ H ₉ 〃 〃 〃 18 C ₃ H ₆ Ph C ₂ H ₅ 〃 〃 〃 19 C ₃ H ₆ OCH ₃ C ₃ H ₆ OCH ₃ 〃 〃 〃 20 C ₂ H ₄ CNC ₂ H ₅ 〃 〃 〃 21 C ₂ H ₄ OH 〃 〃 〃 〃 22 C ₂ H ₄ Cl C ₂ H ₄ Cl 〃 〃 〃 23 C ₂ H ₄ 〃 OP H 24 C ₂ H ₄ OCO ₂ CH ₃ C ₂ H ₄ OCO ₃ CH ₃ 〃 〃 〃 25 C ₂ H ₄ OCOCH ₃ C ₂ H ₄ OCOCH ₃ 〃 〃 〃 26 C ₂ H ₄ OCH ₂ CH = CH ₂ H 〃 〃 27 C ₆ H ₁₁ (cyclohexyl) H undefined undefined undefined 28 morpholine ring undefined undefined undefined 29 piperidine ring undefined undefined undefined 30 C ₃ CH ₃ undefined undefined _{O 31 C 2 H 5 C 2} H 5 4 over CH ₃ undefined undefined 32 undefined undefined 3-Cl 4-Cl 〃 33 undefined undefined _{4-C 3 H 7 (i} ) H 〃 34 undefined undefined 4- Br 〃 〃 35 CH ₂ CH = CH ₂ CH ₂ CH = CH ₂ H 〃 〃 36 CH ₂ Ph C ₂ H ₅ 〃 〃 〃 37 C ₄ H ₉ C ₄ H ₉ 〃 〃 38 C ₂ H ₄ OCH ₃ C ₂ H ₄ OCH ₃ 〃 〃 〃 39 C ₂ H ₄ OC ₄ H ₉ C ₂ H ₄ OC ₄ H ₉ 〃 〃 〃 40 C ₃ H ₆ OCH ₃ C ₃ H ₆ OCH ₃ 〃 〃 〃 41 C ₂ H ₄ OCOCH ₃ C ₂ H ₄ OCOCH ₃ 〃 〃 〃 42 C ₂ H ₄ OCO ₂ C ₂ H ₅ C ₂ H ₄ OCO ₂ C ₂ H ₅ 〃 〃 〃 43 C ₂ H ₄ CN C ₂ H ₅ 〃 〃 〃 44 C ₂ H ₄ Br 〃 〃 〃 〃 45 C ₂ H ₅ 〃 4-OCH ₃ 〃 NHCO 46 〃 〃 4-CH ₃ 〃 〃 47 〃 〃 3-CH ₃ 〃 〃 48 〃 3-〃 l 〃 〃 49 〃 〃 4-Cl 〃 〃 〃 〃 3-Cl 〃 (however, Ph means a phenyl group, and (i) means iso indicating branching). )

[0091]

EFFECT OF THE INVENTION A useful ink composition having excellent dispersion stability for a long period of time, excellent ink jet printing suitability for hydrophobic fibers and giving a clear yellow printed material was 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 front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // C09B 57/02 D 7306-4H

Claims (4)

[Claims] 1. An ink composition for ink-jet printing for hydrophobic fibers containing at least one disperse dye represented by the general formula (1). (In the formula (1), R ₁ and R ₂ are 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 ₁ and R ₂ may together form a heterocyclic residue. R ₃ and R ₄ each represent a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an alkoxy group, and X represents NH, O or NHCO. Here, the alkyl group and the alkoxy group mean those having 1 to 4 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 for inkjet printing according to any one of claims 1 to 3.