JPH07278482A - Ink composition for ink-jet printing and method for dyeing with the same - Google Patents

Abstract

PURPOSE:To improve long-term dispersion stability, suitability for ink-jet printing, clearness, and dyeing properties by mixing a specific coumarin compound with water and a hydrophilic organic solvent. CONSTITUTION:A 7-dialkylamino-3-formyl-4-chlorocoumarin represented by formula I (wherein R1 and R2 each is H or a 1-4C alkyl) is condensed with cyanomethylbenzimidazole, represented by formula II, at 70-110 deg.C in the presence of pyridine, N,Ndimethylformamide, etc., to obtain a coumarin compound (a) represented by formula III. 1-30wt.% the compound (a) is wetpulverized together with a small amount of water and a nonionic or anionic surfactant, the amount of the surfactant being 0.2-5 times the amount of the compound (a), to reduce the average particle diameter of the compound (a) to 3mum or smaller. To the resultant mixture are added water and 1-50wt.% hydrophilic solvent. Thus, the objective composition is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition for ink jet printing and a method for dyeing hydrophobic fibers using the same. 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 has a coloring material (dye) and a liquid medium (water or various organic solvents or a mixture thereof) for dispersing the coloring material 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 a disperse dye 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, which contains at least one coumarin-based compound represented by the formula (1).

[0012]

[Chemical 2]

(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) (2) The coumarin-based compound represented by the formula (1) The ink composition for inkjet printing as described in the item (1), wherein occupies 50% by weight or more of the bulk powder of the dye. (3) The ink composition for inkjet printing as described in the above item (1), which contains water and a hydrophilic organic solvent. 4) A method for dyeing a hydrophobic fiber, which comprises using the ink composition according to any one of items (1) to (3) above.

The coumarin-based compound of the above formula (1) is capable of dyeing hydrophobic fibers, for example, polyethylene terephthalate fibers, with a bright yellow or orange color having fluorescence. (Japanese Patent Application No. 5-103757).

The compound represented by the formula (1) used in the present invention is, for example, the compound represented by the formula (2)

[0016]

[Chemical 3]

(In the formula, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 7-dialkylamino-3-formyl-4
-Chlorocoumarin and formula (3)

[0018]

[Chemical 4]

A known cyanomethylbenzimidazole represented by the following is preferably used as a solvent with alcohols such as isopropyl alcohol, n-butyl alcohol and cyclohexanol, ethers such as dioxane, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. Can be obtained by heat condensation in the presence of pyridine, N, N-dimethylformamide, dimethylsulfoxide or the like, preferably at 70 to 110 ° C.

The coumarin-based compound represented by the general formula (1) is, for example, a compound in which R ₁ and R ₂ are both methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group or isobutyl group, or R Examples include compounds in which ₁ is a methyl group, R ₂ is an ethyl group, R ₁ is a methyl group, R ₂ is an n-propyl group, R ₁ is an ethyl group and R ₂ is an n-butyl group.

The coumarin compounds represented by the above formula (1) used in the present invention may be used alone or as a mixture, and may be used for adjusting a desired hue or improving fastness and dyeability. It is also possible to mix and use several kinds of 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 (dispersed). Alternatively, each dye may be dispersed and blended to produce an ink composition for inkjet printing. The coumarin-based compound represented by the formula (1) is 50% of the dye content.
It is preferable to use it so as to be more than weight%. The blending ratio of other dyes optionally blended 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 compound of the formula (1) used.

Other disperse dyes that can be blended include azo dyes, anthraquinone dyes, quinophthalone dyes,
Examples thereof include benzopyran dyes, thioindigo dyes, benzodifuranone dyes, benzoxanthene dyes, benzanthrone dyes and methine disperse dyes.

In the ink composition of the present invention, the amount of the bulk dye powder containing at least one compound represented by the formula (1) is 1 to 30% by weight, preferably 2 to the total weight of the ink liquid. It 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 solvent, polyalkylene glycols such as polyethylene glycol and polypropylene glycol; alkylene glycols such as ethylene glycol, 3-methylpentane-1,3,5-triol, propylene glycol and butylene glycol; glycerin; N-methyl-2. Examples include nitrogen-containing heterocyclic ketones such as -pyrrolidone and 1,3-dimethyl-2-imidazolidinone. These can be used as a mixture of two or more kinds.

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, anionic or nonionic surfactant is used to make fine particles (dispersion).
Preference is given to using the dyestuffs mentioned. Examples of anionic surfactants that can be used for making the dye fine particles include:
Lignin sulfonic acid, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkylnaphthalene sulfonic acid, formalin condensate of special aromatic sulfonic acids,
Formalin condensate of creosote oil sulfonic acid and the like can be mentioned. 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 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 more of the above surfactants or a mixture thereof and a small amount of water are added to the bulk powder of the compound represented by the above formula (1), and a sand grinder is used. Alternatively, it may be wet-milled sufficiently using a sand mill or the like so that the average particle size of the dye is 3 μm or less, preferably about 0.1 μm or less, and a nonionic or anionic surfactant is added if necessary, and water and After diluting to a desired dye concentration with a hydrophilic organic solvent, dyes, dusts, foreign substances and the like having a large particle size are removed by passing through a filter as needed, and then used. When a nonionic or anionic surfactant is used, it is 0.05 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the ink composition.
It is contained in the range of.

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 has particularly good stability among various characteristics, and it can be stored for a long period of time. Has no sedimentation,
Moreover, it is also characterized in that the discharge orifice is not clogged. In addition, antibacterial and antifungal agents (for example, Deltop manufactured by Takeda Pharmaceutical Co., Ltd.) can be added.

To dye hydrophobic fibers such as polyethylene terephthalate (white cloth) using 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 60 ° C.
After drying at 100 to 100 ° C, it is usually 100 to 200 ° C.
1 minute to 20 ° C., preferably 160 to 180 ° C.
The desired dyed product can be obtained by holding for 5 minutes, preferably 5 to 10 minutes to develop a color (high temperature atmospheric pressure steaming fixing method), and then performing reductive washing. Further, the woven cloth to be dyed with a water-soluble polymer or the like can be pretreated in order to quickly absorb and retain the ink composition of the present invention.

[0030]

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.

Production Example 7-Diethylamino-4-chloro-3-formylmarin 14 parts, isopropyl alcohol 150 parts, cyanomethylbenzimidazole 8 parts and pyridine 4 parts at 100 ° C.
React for 5 hours. After completion of the reaction, the mixture is cooled to room temperature and filtered. The obtained cake was washed with isopropyl alcohol to obtain the following formula (4).

[0032]

[Chemical 5] 17.5 parts of a coumarin compound represented by m.
p. 265-267 ° C (DSC)

Example 1 10 parts of a bulk powder of the coumarin-based dye represented by the above formula (4), 15 parts of a formalin condensate of methylnaphthalenesulfonic acid and 50 parts of water, which were obtained by synthesizing according to the above-mentioned production example, were mixed with glass beads 100. Wet grinding was carried out for 48 hours in a sand mill in the presence of a capacity part to form fine particles. The glass beads were removed by filtration to obtain 70 parts of a dispersion liquid. 2 parts of a block copolymer of ethylene oxide and propylene oxide, 5 parts of glycerin
5 parts and 60 parts of water were added to obtain an ink composition having a dye concentration of 5%. This was further passed through a 10-micron filter to remove large dye particles, foreign matters and the like to obtain a 5% ink composition having an average particle size of 0.05 micron for inkjet printing. The ink composition for inkjet printing obtained in this example has a room temperature or a low temperature (0 degree Celsius).
In addition, the product showed good stability 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. Fastness to light was grade 5 [carbon arc lamp method, 20 hours, 40 hours, discoloration and fading JIS
Blue scale for JIS discoloration (Grade 1
Displayed as (defective) to grade 5 (excellent)].

Example 2 The following formula (5) obtained by synthesis in the same manner as in the above Production Example

[0036]

[Chemical 6]

12 parts of powdered coumarin-based dye of 18 parts, 18 parts of formalin condensate of naphthalene sulfonic acid, 5 parts of lignin sulfonic acid and 70 parts of water were wet-milled for 50 hours in a sand mill in the presence of 100 parts by volume of glass beads. Made into 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 48
And 46 parts of ion-exchanged water were added to obtain a 7.5% 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 yellow color was obtained. This was a beautiful dyeing without bleeding.

Example 3 The following formula (6) obtained by synthesis in the same manner as in Production Example

[0040]

[Chemical 7]

12 parts of bulk powder of coumarin type dye represented by the formula, 15 parts of formalin condensate of naphthalene sulfonic acid, 5 parts of lignin sulfonic acid and 68 parts of water are wet pulverized in a sand mill for 48 hours in the presence of 100 parts by volume of glass beads. Made into fine particles. The glass beads were removed by filtration to obtain 90 parts of a dispersion liquid. Nonylphenol ethylene oxide 8
2 parts of a 5 mol addition product, 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 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 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 18 parts of a 1: 1 mixture of coumarin dye bulk powders represented by the above formulas (4) and (6) obtained by synthesis in the same manner as in Production Example, formalin condensate of naphthalenesulfonic acid 18
Parts, 4 parts of lignin sulfonic acid and 60 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. 0.5 parts of a block copolymer of ethylene oxide and propylene oxide, 40 parts of glycerin and 31.5 parts of ion-exchanged water were added thereto to obtain an ink composition having an average particle size of 0.1 micron 10%. The ink composition for inkjet printing obtained in this example is
It showed good stability at room temperature or low temperature (0 degree Celsius) 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 yellow color was obtained. This was a beautiful dyeing without bleeding.

Example 5 The formula (4) obtained by the synthesis of the production example and the formula (7) synthesized by the known method.

[0046]

[Chemical 8]

18 parts of a 3: 1 mixture of coumarin-based dye powder, 10 parts of a formalin condensate of naphthalene sulfonic acid, 6 parts of lignin sulfonic acid and 66 parts of water were mixed in a sand mill in the presence of 100 parts by volume of glass beads to give 40 parts. It was wet-milled for a time 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, 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 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 part was colored bright yellow was obtained. This was a beautiful dyeing without bleeding.

Examples 6 to 10 The following formula (8) synthesized by the same method as in the above-mentioned production example.

[0050]

[Chemical 8]

A compound having the structure represented by the formula ( ₁₎ and R ₁ and R ₂ having the structures shown in the following table was synthesized, an ink composition was prepared in the same manner as in Example 1, and these inks were used to produce on demand. It is possible to obtain a dyed product which is printed on a polyester fiber with a type inkjet printer and has a bright yellow color without bleeding.

Example R ₁ R ₂ 6 CH ₃ CH ₃ 7 〃 C ₄ H ₉ -n 8 C ₂ H ₅ 〃 9 〃 C ₃ H _7- i 10 〃 C ₄ H ₉ -n

[0053]

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 bright yellow to orange print having fluorescence was obtained.

Claims (4)

[Claims] 1. An ink composition for inkjet printing for hydrophobic fibers containing at least one coumarin-based compound represented by the following formula (1): (In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2. The ink composition for inkjet printing according to claim 1, wherein the coumarin-based compound represented by the formula (1) accounts for 50% by weight or more of the bulk powder of the dye. 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.