JPH0527667B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an ink jet printing ink using a reactive disperse dye. More specifically, the present invention relates to inkjet printing inks using reactive disperse dyeing, specific nonionic surfactants, anionic surfactants, and organic acid salts. 2. Description of the Related Art Conventionally, so-called inkjet recording methods have been known in which recording is performed by ejecting ink droplets from minute ejection orifices. In addition, an ink has been proposed for inkjet printing of polyester cloth by dissolving the disperse dye in a solution consisting of an organic solvent capable of dissolving the disperse dye, water, and a water-soluble resin and having a surface tension of 40 dyne/cm or more (specially Publication No. 59108). However, simultaneous inkjet printing of a blended fabric of polyester fibers and cellulose fibers has not yet been solved. Problems to be Solved by the Invention The present invention provides an inkjet printing ink that can simultaneously print a blended fabric of polyester fibers and cellulose fibers using a reactive disperse dye, a specific surfactant, and an organic acid salt. Its purpose is to provide. Means for solving the problems, that is, the present invention has the general formula [] (In the formula, D represents a water-insoluble dye residue, X represents an oxygen atom or -NH- group, Y represents ^OR3 or ^NR4R5 , and ^R3 , ^R4 and ^R5 are hydrogen atoms ^. or an alkyl group that may have a substituent,
Represents an aryl group or an aralkyl group,
or a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ⁴ and R ⁵ ) water-insoluble or sparingly soluble reactive disperse dye 1 to 30
% by weight and a mixture of a nonionic surfactant and an anionic surfactant from 0.2 to 75% by weight, and the inkjet printing ink is adjusted to pH 6.5 to 7.5 using an organic acid salt. . In the ink of the present invention, the water-insoluble or releasable reactive disperse dye D represented by the general formula [] includes anthraquinone, azo, quinophthalone, methine, and heterofused ring systems. The amount of the reactive disperse dye used in the ink of the present invention is in the range of 1 to 30% by weight, preferably in the range of 3 to 15% by weight. The nonionic surfactant in the ink of the present invention has the following general formulas [] and [] (In the formula, R ¹ and R ² represent a hydrogen atom or an α-methylbenzyl group, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom, a methyl group, or an α-methylbenzyl group. , R ¹ ,
Either one of R ² and R ⁴ represents an α-methylbenzyl group. and m is an integer from 7 to 150) CH ₃ O-(CH ₂ CH ₂ O-) _o H...[] (In the formula, n represents 6 to 30) A nonionic surfactant represented by can be mentioned. In the nonionic surfactant represented by the above general formula [], the number m of added moles of ethylene oxide
is in the range of 7 to 150, preferably
A range of 10 to 100 is mentioned. The nonionic surfactant represented by the above general formula [] can be easily produced, for example, by reacting a mixture of meta- and para-cresol or phenol with styrene, ethylene oxide, etc., by a known method. In addition, the amount used in the ink is in the range of 0.2 to 15% by weight, preferably 0.5 to 10% by weight.
The range of In the nonionic surfactant represented by the above general formula [], the number of added moles of ethylene oxide n
is in the range of 6 to 30, preferably 7
~10 ranges are mentioned. The nonionic surfactant represented by the above general formula [] is easily produced by reacting methanol with ethylene oxide or the like. The amount used in the ink is 2.5 to 75% by weight, preferably 8 to 40% by weight. The anionic surfactant in the ink of the present invention has the following general formula [] (wherein M represents a sodium, potassium or ammonium salt). The anionic surfactant represented by the above general formula [] can be easily produced by, for example, a known method by causing a condensation reaction between naphthalene sulfonic acid and formaldehyde. In addition, the amount used in the ink is in the range of 0.2 to 15% by weight, preferably 0.5 to 10% by weight.
The range of Furthermore, the amount of the mixture of the nonionic surfactant and anionic surfactant used in the ink of the present invention is
A range of 0.2 to 75% by weight is mentioned, preferably 0.5
-40% by weight. Examples of the organic acid salts represented by the above general formula [] include the following organic acids such as NH ₄ , Na,
Examples include salts such as K, N(CH ₃ ) ₃ and the like. Formic acid HCOOH Acetic acid CH ₃ COOH Benzoic acid C ₆ H ₅ COOH Phthalic acid C ₆ H ₅ (COOH) _2Lactic acid CH ₃ CH(OH)COOH Oxalic acid (COOH) _2Succinic acid (CH ₂ COOH) ₂ Ammonium carbamate H ₂ NCOOH The pH prepared using the organic acid salt represented by the above general formula [] is in the range of 6.5 to 7.5, preferably in the range of 6.8 to 7.2. The ink of the present invention can be obtained by dispersing or dissolving the above-described reactive disperse dye, nonionic surfactant, anionic surfactant, and organic acid salt in water. The amount of water used in the ink of the present invention is 30% by weight or more, preferably 50 to 85% by weight.
The range of In addition, up to 50% by weight of an anti-drying agent, an antifoaming agent, a hydrotrope, etc. may be added to the ink of the present invention. Since the ink of the present invention passes through a fine nozzle with a diameter of 10 to 100 μm, even better results can be obtained by performing a filtering step after production to remove coarse particles. For example, the ink of the present invention includes a finely ground reactive disperse dye that is insoluble or releasable in water, a nonionic surfactant represented by the above general formulas [] and [], and a nonionic surfactant represented by the above general formula []. Anionic surfactants and organic acid salts, as well as anti-drying agents, anti-foaming agents, hydrotropes, etc., are added to the water as necessary, and the dye is mixed using a pulverizer such as a sand grinder or paint conditioner. 0.005～
It can be obtained by grinding and dispersing particles of 10μ, preferably 0.005 to 1μ. Functions and Effects The reactive disperse dye in the ink of the present invention has a group that reacts with cellulose fibers, so it can dye cellulose fibers, and has a disperse dye structure that is insoluble or poorly soluble in water. Because of this, polyester fibers can be dyed.
That is, the dye can dye cellulose fibers and polyester fibers. In the present invention, a nonionic surfactant represented by the general formula [] is used as a dye solubilizer, and the pH is adjusted to 6.5 to 7.5 with an organic acid salt represented by the general formula [] as a dye/fiber activator. It is thought that this improves the dyeing of cellulose fibers. Furthermore, by using the nonionic surfactant represented by the general formula [] and the anionic surfactant represented by [] of the present invention, the dye is efficiently made into fine particles, and an ink with long-term dispersion stability can be obtained. It is believed that an inkjet printing ink can be obtained in which clogging of the nozzle, dry adhesion to the periphery of the nozzle tip, and bleeding of the printed fabric are suppressed. Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples. In addition, various evaluation methods in Examples are as follows. (1) Viscosity The viscosity of the ink was measured using a BL type viscometer manufactured by Tokyo Keiki Seisaku Co., Ltd. under the following conditions. Measurement temperature: 25℃ Rotor used: No. 1 Rotor rotation speed: 60 rpm (2) Particle size After over-processing the ink using viscous paper No. 60 manufactured by Toyo Paper Co., Ltd., the particle size was determined using the following equipment. was measured. Particle size measuring device: Submicron Particle Analyzer N-4 (manufactured by Coulter) Measured particle size range: 0.003 to 3 μ (3) Dispersion rate Transfer the ink to a 100 ml graduated cylinder, let it stand at room temperature for 7 days, then add 10 ml from the top of each cylinder. Remove 10ml from the bottom. Dilute 05g of this extracted ink with water.
Make 100ml of dye aqueous solution, take 1ml of this dye aqueous solution, and add 80% acetone aqueous solution (0.1% acetic acid)
Dilute to 100ml. The absorbance at the maximum absorption wavelength of this solution, λmax, is measured. Then, the dispersion rate was calculated using the following formula. Absorbance of upper dye aqueous solution/absorbance of lower dye aqueous solution x 100 = dispersion rate (%) (4) Stability The following test was conducted using the ink. (a) Heating Stability and Cooling Stability The fluidity and particle stability of the ink were observed after it was kept in a constant temperature bath for 1 hour under the following temperature conditions. Heating temperature: 60°C Cooling temperature: -15°C Evaluation was made as follows. ○ Good △ ←-→ × Poor (b) Stability over time The ink was stored at room temperature for 180 days, and the presence or absence of sedimentation of dye particles was observed and evaluated as follows. Good ○ △ ←―→ × Poor (5) Inkjet printing method, evaluation method for bleeding of printed fabric, and deep color measurement method (a) Inkjet printing method Polyester/ After drawing on a cellulose blend broadcloth (65/35 weight ratio), it was dried at 100°C for 30 seconds. Next, this was treated with a high temperature and normal pressure steam fixing method (185°C x 7 minutes) and then washed with alkali to obtain a printed cloth. (b) Method for evaluating bleeding of printed fabric The outline of the image of the printed fabric obtained by method (a) of (6) above was observed under a microscope at 100 magnification, and the degree of bleeding was evaluated as follows. ○ No bleeding △ ←―→ × Large bleeding (c) Dark color measurement method The surface reflectance of the polyester/cellulose blend printed fabric obtained by method (a) in (5) above was measured using a color difference meter (Nippon Denshoku Kogyo Co., Ltd.). (manufactured by the same company). Furthermore, one side of the blended printed fabric was dissolved in the following manner, and the surface reflectance of the undissolved remaining fabric was similarly measured using a color difference meter. Dissolution of polyester side: Immerse in hexafluoroisopropanol and dissolve at room temperature for 4 hours. Cellulose side dissolution: 97% sulfuric acid: water (55:45
(volume ratio) in an aqueous solution and treated at room temperature for 12 hours. (6) Evaluation method for nozzle clogging and dry adhesion around the nozzle tip The following evaluation was performed using ink. (a) Evaluation method for nozzle clogging Apply 3.5ml/hr of ink to a nozzle with a diameter of 100μ.
The discharge was observed from the nozzle tip. After ejecting for 1 hour, it was stopped for 1 hour, and ejecting was performed again, and the ejection response time at this time was measured. The ejection stability was examined from the change in the ejection speed during the first hour and the change in the re-ejection speed after stopping for one hour. Nozzle clogging was evaluated from the above-mentioned ejection response time and ejection stability. Discharge stability ○ Good △ ←―→ × Poor Discharge response time ○ 0 seconds △ ←10 seconds → × No discharge (b) Evaluation method for dry adhesion around the nozzle tip Method (a) in (6) above After discharging for 1 hour, stopping for 1 hour, and discharging again for 1 hour, the area around the nozzle tip was observed under a microscope with a magnification of 100, and the dry adhesion amount was evaluated as follows. Dry adhesion ○ None △ ← Small amount → × Large amount Examples 1 to 4 The following composition Reactive disperse dye [Structural formula (a), (b), (c) or
Dye indicated by (d)] CH ₃ O― (CH ₂ CH ₂ O―) ₈ H 25g CH ₃ COONa aqueous solution PH7 adjusted water A total of 100 g of the mixture was ground at room temperature in a sand grinder to prepare an ink. Using the ink obtained above, various physical properties of the ink, bleeding and dark color of the printed fabric, and nozzle clogging and drying around the nozzle tip were determined according to the methods (1) to (6) above. As a result of examining the adhesion, all were found to be good as shown in Table 1.

【table】

【table】

Claims (1)

[Claims] 1. General formula [] (In the formula, D represents a water-insoluble dye residue, X represents an oxygen atom or -NH- group, Y represents ^OR3 or ^NR4R5 , and ^R3 , ^R4 and ^R5 are hydrogen atoms ^. or an alkyl group that may have a substituent,
Represents an aryl group or an aralkyl group,
or a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ⁴ and R ⁵ ) water-insoluble or sparingly soluble reactive disperse dye 1 to 30
An inkjet printing ink containing 0.2 to 75% by weight of a mixture of a nonionic surfactant and an anionic surfactant, and adjusted to a pH of 6.5 to 7.5 using an organic acid salt. 2. In the ink jet printing ink according to claim 1, the nonionic surfactant has the general formula [] (In the formula, R ¹ and R ² represent a hydrogen atom or an α-methylbenzyl group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group, or an α-methylbenzyl group, and R ¹ , R ² and R ⁴ represent an α-methylbenzyl group, and m represents an integer of 7 to 150) and the general formula [] CH ₃ O (—CH ₂ CH ₂ O—) _o H...[] (In the formula, n represents 6 to 30) An ink that is a nonionic surfactant. 3. In the ink jet printing ink according to claim 1, the anionic surfactant has the general formula [) An ink which is an anionic surfactant represented by the formula (wherein M represents a sodium, potassium or ammonium salt). 4 In the inkjet printing ink described in claim 1, the organic acid salt has the general formula [] (In the formula, R represents a carbon atom, an aliphatic group having 1 to 6 carbon atoms, or an aromatic group. X represents a hydroxyl group or an amino group, and M represents _NH4 , K, Na, ( _CH3 ) _3N . and a is 0-1, b is 0-2, C is 0-2
An ink that is an organic acid salt represented by 5. The inkjet printing ink according to claim 1, which has a pH of 6.8 to 7.2, which is adjusted using an organic acid salt.