JPH0535741B2 - - Google Patents

Description

[Detailed description of the invention]

Object of the Invention (a) Industrial Application Field The present invention relates to an inkjet printing ink using a reactive disperse dye. More specifically, the present invention relates to an inkjet printing ink using a reactive disperse dye using a specific nonionic surfactant or anionic surfactant and a polyphosphate. (B) Prior Art Conventionally, a so-called inkjet recording method has been known in which recording is performed by ejecting ink droplets from a minute ejection orifice. 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). (c) Problems to be Solved by the Invention However, simultaneous inkjet printing of a blended fabric of polyester fibers and cellulose fibers has not yet been solved. (d) Objective 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 a polyphosphate. Its purpose is to Structure of the Invention (a) Means for Solving the Problems That is, the present invention provides: (1) A water-insoluble or sparingly soluble reactive disperse dye represented by the general formula [] (In the formula, D represents a water-insoluble dye residue;
represents an oxygen atom or -NH- group; Y is
Represents OR ³ or NR ⁴ R ⁵ ; R ³ , R ⁴ and R ⁵
represents a hydrogen atom or an alkyl group, aryl group or aralkyl group which may have a substituent, or represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ⁴ and R ⁵ ) containing 1 to 30% by weight and 0.2 to 75% by weight of a mixture of nonionic surfactants and anionic surfactants, and using polyphosphate to achieve a pH of 6.5 to
Inkjet printing ink adjusted to 7.5. (2) Nonionic surfactants have 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 ,
Either one of R ² and R ⁴ represents an α-methylbenzyl group, and n represents an integer of 7 to 150) or the general formula [] CH ₃ O (-CH ₂ CH ₂ O-) _o H ...[] (wherein n represents 6 to 30) The inkjet textile printing ink according to claim 1. (3) The anionic surfactant has the general formula [] The inkjet printing ink according to claim 1, wherein M represents a sodium, potassium or ammonium salt. (4) The inkjet printing ink according to claim 1, wherein the polyphosphate is a sodium or potassium salt of hexametaphosphoric acid or pentapolyphosphoric acid. (5) The inkjet textile printing ink according to claim 1, which has a pH in the range of 6.5 to 7.5. The gist is as follows. The water-insoluble or sparingly soluble reactive disperse dye used in the present invention is represented by the above general formula [], and D includes anthraquinone series, azo series, quinophthalone series, methine series, heterofused ring systems, etc. be able to. By inkjet printing these three primary colors, together with black obtained from these three primary colors, four colors are created, so-called
Can be printed in full natural colors. The amount of reactive disperse dye used in the ink of the present invention can be in the range of 1 to 30% by weight,
A preferable range is 3 to 15% by weight. 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. Moreover, [] is easily produced by reacting methanol with ethylene oxide or the like. Further, the number n of moles of ethylene oxide added in the general formula [] of the present invention can be listed in the range of 7 to 150, preferably in the range of 10 to 100. Furthermore, the amount used can be in the range of 0.2 to 15% by weight, preferably 0.5% by weight.
A range of up to 10% by weight may be mentioned. Also.
Number of moles of ethylene oxide added in general formula [] n
can be listed in the range of 6 to 30, preferably in the range of 7 to 10. Furthermore, the amount used can range from 2.5 to 75% by weight, preferably from 8 to 40% by weight. The anionic surfactant represented by the above general formula [] can be easily produced by, for example, a known method by subjecting naphthalene sulfonic acid to a condensation reaction with formaldehyde. Furthermore, the amount used can be in the range of 0.2 to 15% by weight,
A preferable range is 0.5 to 10% by weight. The total amount of the mixture of the above nonionic surfactant and anionic surfactant used can range from 0.2 to 75% by weight, preferably from 0.5 to 40% by weight. Furthermore, polyphosphates may include sodium or potassium salts of hexametaphosphoric acid and pentapolyphosphoric acid. In addition, the pH adjustment with the polyphosphate of the present invention is 6.5.
~7.5. Preferably, 6.8 to 7.2 can be mentioned. The ink of the present invention can be obtained by dispersing/dissolving the above-mentioned reactive disperse dye, a surfactant of general formulas [], [], and [], and a polyphosphate in water. Furthermore, the ink of the present invention can be obtained by dispersing/dissolving the above-mentioned reactive disperse dye, a surfactant represented by the general formulas [], [], and [] and a polyphosphate in water, The amount of water used is 30% by weight or more, preferably 50 to 85% by weight.
The range of Furthermore, 50% by weight or less of an anti-drying agent, an antifoaming agent, a hydrotrope agent, 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 contains a finely ground reactive disperse dye that is insoluble or sparingly soluble in water, a surfactant of the general formulas [], [], and [], and a polyphosphate, and optionally a drying prevention agent. Add agents, antifoaming agents, hydrotropes, etc. to water, and use a fine grinder such as a sand grinder or paint conditioner to grind the dye to 0.005~10μ, preferably
It can be obtained by crushing and dispersing it into particles of 0.005 to 1μ. (B) Effect The reactive disperse dye of the present invention has a group that reacts with cellulose fibers, so it dyes cellulose fibers, and since it has a disperse dye structure that is insoluble or poorly soluble in water, it can be used to dye cellulose fibers. Dye the fibers. After all, it is possible to dye two types of fibers with one dye. In particular, in the present invention, in order to improve the dyeing of cellulose fibers, the general formula []
The pH is adjusted to 6.5-7.5 using polyphosphate as a nonionic surfactant and dye/fiber activator. Furthermore, by using the surfactants of the general formulas [] and [] of the present invention, the dye can be made into fine particles efficiently and an ink with long-term dispersion stability can be produced. It is considered that an inkjet printing ink was obtained in which dry adhesion to the periphery of the nozzle tip and bleeding of the printed fabric were suppressed. (c) Examples and Effects 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 under the following conditions using a BL viscometer manufactured by Tokyo Keiki Seisaku Co., Ltd. Measurement temperature: 25℃ Rotor used: No. 1 Rotor rotation speed: 60 rpm (2) Viscosity After over-processing the ink using viscous paper No. 60 manufactured by Toyo Paper Co., Ltd., using the following equipment, Particle size was measured. Particle size measuring device: submicron particle analyzer
N-4 (manufactured by Coulter) Measured particle size range: 0.003 to 3μ (3) Dispersion rate Transfer the ink to a 100ml graduated cylinder and leave it at room temperature for 7 days, then draw out 10ml from the top and 10ml from the bottom. Dilute 0.5g 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 of this solution at the maximum absorption wavelength 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 left standing at room temperature for 180 days, and the presence or absence of sedimentation of the dye particles was observed and evaluated as follows. ○ Good △ ←−→× Poor (5) Inkjet printing method, evaluation method for bleeding of printed fabric, and dark color measurement method (a) Inkjet printing method Ink was printed on polyester/ After drawing on a cellulose (65/35% by weight) blended broadcloth, 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 the method (5) above was observed under a microscope with a magnification of 100, and the degree of bleeding was evaluated as follows. ○ No bleeding △ ←−→× Large bleeding (c) Hyperchromic measurement method The surface reflectance of the polyester/cellulose blend printed fabric obtained by method (a) of (5) above was measured using a color difference meter (manufactured by Nippon Denshoku Co., Ltd.). ). Furthermore, one side of the blended printed fabric was dissolved by the following method, and the surface reflectance of the undissolved remaining fabric was measured in the same manner. Dissolution of Γ polyester side Immerse in hexafluoroisopropanol and treat at room temperature for 4 hours. Dissolution of Γ cellulose side Immerse in an aqueous solution of 97% sulfuric acid and 55:45 water (volume ratio) and treat 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 discharging for 1 hour, stop for 1 hour,
Discharge was performed again, and the discharge 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 Reactive disperse dye with the following composition [Formula below (each of A to D alone)]
5g 2g CH ₃ O (-CH ₂ CH ₂ O-) ₈ H 25g 1 g Sodium hexametaphosphate Aqueous sodium pentapolyphosphate solution PH7-adjusted water Remaining amount 100 g of the mixture was ground in a sand grinder at room temperature 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. A water-insoluble or sparingly soluble reactive disperse dye represented by the general formula [] (In the formula, D represents a water-insoluble dye residue; X represents an oxygen atom or -NH- group; Y represents OR ³ or NR ⁴ R ⁵ ; R ³ , R ⁴ and R ⁵ 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 ) 1 to 30% by weight and a nonionic surfactant and anionic interface An inkjet printing ink containing 0.2 to 75% by weight of a mixture with an activator and adjusted to pH 6.5 to 7.5 using a polyphosphate. 2 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 n represents an integer of 7 to 150) or the general formula [] CH ₃ O (—CH ₂ CH ₂ O—) _o H ... [ ] (wherein n represents 6 to 30) The inkjet printing ink according to claim 1. 3 The anionic surfactant has the general formula [] The inkjet printing ink according to claim 1, wherein M represents a sodium, potassium or ammonium salt. 4. The inkjet textile printing ink according to claim 1, wherein the polyphosphate is a sodium or potassium salt of hexametaphosphoric acid or pentapolyphosphoric acid. 5. The inkjet printing ink according to claim 1, which has a pH in the range of 6.5 to 7.5.