JP2007238798A - Ink for inkjet printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ink for inkjet printing excellent in storage property, stability especially when stored for a long time at a low temperature, jetting property, and dye fixing property. <P>SOLUTION: This ink for inkjet printing contains at least a coloring agent, water, and a water-soluble organic solvent, and yet contains nitrilotriacetic acid, and another chelating agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink for ink-jet textile printing, and more particularly to an ink for ink-jet textile printing that has excellent long-term storage stability that does not cause precipitation or sedimentation due to low-temperature storage, and excellent emission stability.

  In recent years, in the field of textile printing, there has been a demand for an ink jet textile printing method that does not require a plate making process in order to shorten the delivery time and cope with small-lot and multi-product production. In the ink jet textile printing method, ink is often stored and used for a long period of time, and it is important to improve its storage stability. At the same time, the emission stability is important, and it is known to purify the dye in order to satisfy these performances.

  For example, it is described that a dye is purified and used to remove a polyvalent metal salt (see, for example, Patent Documents 1 and 2).

  Moreover, in order to suppress the influence of the remaining polyvalent metal ions, it has been studied to use a chelating agent (for example, see Patent Documents 3 and 4).

  However, when a large amount of a chelating agent is blended, there is a problem that the solid content increases and the light emission property is impaired. In particular, in textile printing ink, a large amount of dye is often blended to increase the dyeing density, and when the dye density is high, there is a problem that the low-temperature storage property and the emission property are lowered when a chelating agent is added.

Furthermore, in a dyeing system using acidic ink, as a pretreatment agent, a compound that generates an acid such as ammonium sulfate is preliminarily contained in the fabric, and the acid is generated by evaporating ammonia during steaming to generate an acid. Is fixed to the fabric. At this time, if the ink contains a large amount of a compound having a buffering capacity, the generated acid is consumed and the acidic dye cannot be sufficiently fixed. Therefore, since the chelating agent has a buffering capacity, it has been required to suppress the influence of polyvalent metal ions with the smallest possible addition amount.
JP-A-5-5053 JP 2004-295472 A JP 2000-327976 A JP 2000-290558 A

  The present invention has been made in view of such a situation, and the object of the present invention is to provide an ink for inkjet printing that is excellent in storage stability, in particular, stability when stored at low temperature for a long period of time, emission properties, and dye fixing properties. It is to provide.

  The object of the present invention is achieved by the following configurations.

  1. An ink for ink-jet printing, comprising at least a colorant, water, a water-soluble organic solvent, and containing nitrilotriacetic acid and another chelating agent.

  2. The chelating agent is at least one selected from hydroxyiminodiacetic acid, L-aspartic acid-N, N-diacetic acid, L-aspartic acid diacetic acid, methylglycine diacetate and (S, S) -ethylenediamine disuccinic acid. 2. The ink for ink-jet printing as described in 1 above, which is a compound of the above or a salt of the compound.

  3. 2. The ink for inkjet printing according to 1 above, wherein the chelating agent is hydroxyiminodiacetic acid or a salt thereof.

  4). The ink for inkjet printing according to any one of 1 to 3, wherein the colorant is an acid dye.

  5. 6. The ink for ink-jet printing as described in 4 above, wherein the acid dye has two sulfonic acid groups.

  6). 6. The ink for ink-jet printing as described in 5 above, which contains an acid dye in an amount of 5 to 10% by mass.

  That is, as a result of intensive studies, the present inventor has found an ink for ink jet textile printing that is excellent in preservability and emission properties, particularly stable when stored at a low temperature for a long period of time and has excellent emission properties.

  The ink for ink-jet textile printing according to the present invention has excellent storage stability, in particular, stability when stored for a long time at low temperature, emission properties, and dye fixing properties.

  The chelating agent of the present invention reacts with a metal ion to form a chelate ring. Ring formation occurs by the formation of covalent bonds or coordinate bonds or both.

  Specific examples of the chelating agent having two acidic groups as the ligand include malonic acid, oxalic acid, phthalic acid, glycolic acid, and salicylic acid.

  Specific examples of the chelating agent having one acidic group and one non-acidic coordination group as a ligand include 8-quinolinol, acetylacetone, trifluoroacetone, dimethylglyoxime, dithizone, and salicylaldehyde.

  Specific examples of the chelating agent having two non-acidic coordination groups as the ligand include, for example, ethylenediamine, 2,2'-bipyridine, and 1,10-phenanthroline. Examples of aminopolycarboxylic acid include ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, butylenediaminetetraacetic acid, pentylenediaminetetraacetic acid, and sodium or ammonium salts thereof. The mass ratio of the chelating agent is 0.01 to 5% by mass in the composition of the ink jet recording liquid.

  Examples of the colorant in the present invention include disperse dyes, reactive dyes, acid dyes, direct dyes, pigments, and oil-soluble dyes. In the present invention, any colorant can be used, but when the fabric is a material such as cotton or silk, an ink composed of a reactive dye and an aqueous medium is preferably used. Nylon, wool, silk, rayon, etc. In the case of these materials, an ink composed of an acid dye, a direct dye and the like and an aqueous medium is preferably used.

  When the fabric is a polyester material, an ink composed of a dispersible dye and an aqueous medium is preferably used. When the colorant is water-insoluble, such as a disperse dye, an oil-soluble dye, or a pigment, it is preferably used in a state of being finely dispersed in water using a dispersant.

  In the present invention, it is particularly preferable to use an acid dye having low solubility in water, and particularly preferably a dibasic acid or a monobasic acid dye.

  Specific compounds of preferred acid dyes for the present invention are shown below. However, the present invention is not limited to these exemplified compounds.

Preferred acid dyes for the present invention are:
C. I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 67, 72, 73, 79 , 99,104,159,169,176,184,193,200,204,207,215,219219: 1,220,230,232,235,241,242,246,
C. I. Acid Orange 3, 7, 8, 10, 19, 22, 24, 51, 51S, 56, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140 , 142, 144, 149, 152, 156, 162, 166, 168,
C. I. Acid Red1,6,8,9,13,18,27,35,37,52,54,57,73,82,88,97,97: 1,106,111,114,118,119,127,131 , 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289 , 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415,
C. I. Acid Violet 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126,
C. I. Acid Blue1,7,9,15,23,25,40,61: 1,62,72,74,80,83,90,92,103,104,112,113,114,120,127,127: 1 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239 , 258, 260, 264, 277: 1,278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350,
C. I. Acid Green 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109,
C. I. Acid Brown 2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413,
C. I. Acid Black 1, 2, 3, 24, 24: 1, 26, 31, 50, 52, 52: 1, 58, 60, 63, 63S, 107, 109, 112, 119, 132, 140, 155, 172, 187 , 188, 194, 207, 222
Examples of the water-soluble organic solvent of the present invention include polyhydric alcohols (for example, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene glycol, triethylene glycol, Tripropylene glycol, 1,2,4-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 1,2-hexanediol, 1,5-pentanediol, 1,2- Pentanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,3-butanediol, 2 -Methyl-1,3-propanediol, etc.), amines For example, ethanolamine, 2- (dimethylamino) ethanol, etc.), monohydric alcohols (eg, methanol, ethanol, butanol, etc.), polyhydric alcohol alkyl ethers (eg, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol) Monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.), 2,2′-thiodiethanol, amides (eg N N-dimethylformamide), heterocyclics (2-pyrrolidone, etc.), acetonitrile, etc. It is. The amount of the water-soluble organic solvent is preferably 10 to 60% by mass with respect to the total ink mass.
The fabric in the present invention is not particularly limited, and examples thereof include various fiber materials such as cotton, silk, wool, nylon, polyester, rayon, acrylic fiber, and the like, blended fabrics, cross-woven fabrics, nonwoven fabrics, and the like. It may be.

  In the textile printing method of the present invention, it is preferable to remove impurities and dirt adhering to the fabric in order to obtain a uniform dyed product (scouring step). In order to prevent bleeding, it is preferable to apply a pretreatment agent by a pad method, a coating method, a spray method or the like (pretreatment step). Thereafter, an image is formed on the fabric containing fibers that can be dyed with a disperse dye by the ink jet recording method using the ink having the above-described configuration (ink application step), and then the ink is applied. The fabric is heat-treated (coloring step), and the heat-treated fabric is washed (washing step) to complete printing on the fabric and obtain a printed product.

  In the case of the ink-jet printing method of the present invention, natural impurities (oil, fat, wax, pectin, natural pigments, etc.) adhering to the fabric fibers, residues of the chemicals used in the fabric production process (sizing agent, etc.) It is desirable to wash them. As cleaning agents used for cleaning, alkalis such as sodium hydroxide and sodium carbonate, surfactants such as anionic surfactants and nonionic surfactants, enzymes and the like are used.

  The pretreatment is not particularly limited as long as a method suitable for the fiber material and ink is appropriately selected from known methods such as pretreatment of water-soluble polymers on the fabric. For example, it is used for a fabric provided with 0.2 to 50% by mass of at least one substance selected from the group consisting of water-soluble metal salts, polycation compounds, water-soluble polymers, surfactants and water repellents. Therefore, it is possible to prevent a high degree of bleeding, and a high-definition image can be printed on a fabric.

  Moreover, according to the preferable aspect at the time of using an acidic dye, it is preferable that a pretreatment agent comprises the pH adjuster which generate | occur | produces an acid by steaming. Preferable examples of the pH adjusting agent include acid ammonium salts such as ammonium sulfate, ammonium tartrate, or sodium diphosphate. By adding these pH adjusters, there is an advantage that hue stabilization and dyeing properties can be improved. These addition amounts may be appropriately determined in consideration of the dye species and the like, but are preferably about 0.2 to 5% by mass, more preferably about 0.5 to 3% by mass.

  The color development step is a step of developing the original hue of ink by adhering to and fixing the dye in the ink that has only adhered to the fabric surface after printing and is not sufficiently adsorbed and fixed to the fabric. As the method, steaming by steam, baking by dry heat, thermosol, HT steamer by superheated steam, HP steamer by pressurized steam, etc. are used. They are appropriately selected depending on the material to be printed, ink and the like. Further, the printed fabric may be immediately heat-treated or may be heat-treated after a while and may be dried and colored according to the intended use, and any method may be used in the present invention.

  A cleaning step is necessary after the heat treatment. This is because a dye that has not participated in the dyeing remains, resulting in poor color stability and low fastness.

  It is also necessary to remove the pretreatment product applied to the fabric.

  If left as it is, not only the fastness is lowered, but also the fabric is discolored.

  Therefore, cleaning according to the object to be removed and the purpose is essential. The method is selected according to the material and ink to be printed. For example, in the case of polyester, treatment is generally performed with a mixed solution of caustic soda, a surfactant, and hydrosulfite. The method is usually carried out in a continuous type such as an open soaper or in a batch type using a liquid dyeing machine, and any method may be used in the present invention.

  Drying is required after washing. After the washed fabric is squeezed or dehydrated, it is dried or dried using a dryer, heat roll, iron or the like.

  In order to maintain the long-term storage stability of the ink, an antiseptic and an antifungal agent may be added to the ink. Examples of the antiseptic / antifungal agent include aromatic halogen compounds (for example, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, and 1,2-benzisothiazolin-3-one (for example, PROXEL GXL). The present invention is not limited to these.

  In the case of a water-insoluble dye, the ink used in the present invention can be dispersed by mixing a dye, a dispersing agent, a wetting agent, a medium and an optional additive and using a dispersing machine. As the disperser, a conventionally known ball mill, sand mill, line mill, high-pressure homogenizer, or the like can be used.

  It is preferable that a dyeing assistant is included in the inkjet ink for printing used for dyeing by the high-temperature steaming method or the fabric used for printing. The dyeing aid has the effect of making eutectic mixture with the water condensed in the form of cloth when steaming the printed fabric, reducing the amount of water that re-evaporates, and shortening the heating time. Further, this eutectic mixture has the effect of dissolving the dye on the fiber and promoting the diffusion rate of the dye into the fiber. Urea is mentioned as a dyeing assistant.

  In inks used in printers and the like, dissolved gas contained in the ink causes the resolution and clarity of the printed matter to be impaired and causes fine bubbles to be generated. Methods for degassing dissolved gas from the ink are roughly divided into a method of degassing by a physical method such as boiling or decompression, and a chemical method of mixing an absorbent into the ink.

  In the present invention, degassing can be performed by any means. In particular, the method of permeating and removing dissolved gas in the ink by passing the ink through the gas-permeable hollow fiber membrane and reducing the pressure on the outer surface side of the hollow fiber membrane has an adverse effect on the physical properties of the ink. This is preferable because the dissolved gas in the ink can be efficiently removed without giving.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to these.

  Inkjet inks 1 to 15 having the following contents were prepared. As a pH adjuster, 0.1 M sodium hydroxide solution or 0.1 M hydrochloric acid solution was used to adjust the pH to 7.0.

Acid dye (CI Acid Blue 112) 10 parts Ethylene glycol 25 parts Glycerin 10 parts Chelating agent 1 (described in Table 1) Amount described in Table 1 Chelating agent 2 (described in Table 2) Amount described in Table 2 Proxel GXL (Avicia) 0.1 parts pH adjuster As appropriate Ion-exchanged water Remainder

NTA: nitrilotriacetic acid EDTA: ethylenediaminetetraacetic acid HIDA: hydroxyiminodiacetic acid ASDA: L-aspartic acid-N, N-diacetic acid GLDA: L-aspartic acid diacetic acid MGDA: methylglycine diacetic acid EDDS: (S, S) -Ethylenediamine disuccinic acid Low-temperature cooling test 100 g or more of the ink was filtered using a cellulose acetate membrane filter having a mesh size of 0.2 microns, and the filtration pressure when 100 g passed was measured.

  The filtration pressure measured after the ink was prepared and stored at −5 ° C. for 1 month and left at room temperature for 8 hours, and then the ratio of the measured filtration pressure was defined as the filtration pressure ratio.

Emissivity test Nozzle plate surface when the ink prepared is driven continuously for 60 minutes under the driving conditions of a drive frequency of 18 kHz and a droplet velocity of 7 m / s using a share mode type piezo head manufactured by Konica Minolta IJ Co., Ltd. The dirt was observed.

Color development test The prepared ink was pre-treated for acidic dye using a textile printer Nassenger-V manufactured by Konica Minolta IJ Co., Ltd. at 540 dpi × 720 dpi (dpi means the number of dots per 2.54 cm). The fabric (silk twill 16cm) was printed. After steaming with 100 ° C. saturated steam for 40 minutes, it was washed and dried by a known method, and the visual density in status T was measured with an X-rite 938 densitometer (manufactured by X-rite).

It turns out that this invention is excellent in preservability from being excellent in the filterability at the time of low-temperature storage. In addition, it can be seen that the ink of the present invention has little contamination on the surface of the nozzle plate and is excellent in light emission.
Furthermore, it can be seen that the ink of the present invention has a sufficient density.

Claims (6)

An ink for ink-jet printing, comprising at least a colorant, water, a water-soluble organic solvent, and containing nitrilotriacetic acid and another chelating agent. The chelating agent is at least one selected from hydroxyiminodiacetic acid, L-aspartic acid-N, N-diacetic acid, L-aspartic acid diacetic acid, methylglycine diacetate and (S, S) -ethylenediamine disuccinic acid. The ink for inkjet printing according to claim 1, wherein the ink is a compound of the above or a salt of the compound. The ink for inkjet printing according to claim 1, wherein the chelating agent is hydroxyiminodiacetic acid or a salt thereof. The ink for inkjet printing according to any one of claims 1 to 3, wherein the colorant is an acid dye. The ink for ink-jet printing according to claim 4, wherein the acid dye has two sulfonic acid groups. The ink for ink-jet printing according to claim 5, comprising 5 to 10% by mass of an acid dye.