JP2005089500A - Method for producing inkjet ink and method for inkjet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing inkjet ink having excellent jetting properties and preservability and to provide a method for recording. <P>SOLUTION: The method for producing the inkjet ink comprises at least a colorant, a dispersing agent, water and a water-soluble organic solvent. In the method for producing the inkjet ink, the colorant having 0.01-10 mass% of moisture content is used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ink manufacturing method and a recording method for ink jet printing.

  The image printing method by the ink jet method is a method of printing by causing a minute droplet of ink to fly and adhere to a target medium. The ink jet system is advantageous in that its mechanism is relatively simple and inexpensive, and can form high-definition and high-quality images.

  Taking advantage of this ink jet system, printing on fabric, so-called ink jet textile printing, has also been developed. Unlike conventional textile printing, ink jet textile printing does not require the creation of a plate and can quickly form an image with excellent gradation. Furthermore, this is an image forming method that is environmentally superior, such as requiring only a required amount of ink for an image and reducing waste liquid.

  In the field of textile printing, there is a demand for an ink jet textile printing method that shortens delivery time and supports small-quantity, multi-product production. There are various types of ink-jet recording methods. Recently, on-demand recording methods, which are mainly used, are so-called piezo methods (piezoelectric device methods) using piezoelectric elements and thermal jet methods (bubble jet (R) methods). )are categorized.

  As inks used in such a system, inks obtained by dissolving or dispersing various water-soluble dyes or water-insoluble dyes in water or a liquid medium composed of water and a water-soluble organic solvent are known. The performance required for the ink is high density, stable ejection for a long time, long-term storage and storage stability, and more desirably high-definition images.

  For example, an ink jet printing method in which the purity of the disperse dye is defined has been proposed (see, for example, Patent Document 1). In this method, a head that applies thermal energy may be sufficient, but the piezo method is insufficient. In addition, the piezo method repeatedly pressurizes and depressurizes many times during ink ejection, so minute bubbles are likely to occur due to cavitation, causing dot omission and landing position misalignment during ink ejection and degrading print quality such as graininess. It has been known. In general, cavitation is a physical phenomenon in which a liquid evaporates into bubbles when the pressure of the liquid at a certain temperature is lower than the vapor pressure determined by the temperature.

  Therefore, the ink used is usually deaerated, and the amount of gas contained in the ink is reduced as much as possible to prevent the generation of bubbles during ejection. As the degassing treatment, a method of degassing ink under reduced pressure, a method of irradiating ultrasonic waves, and a method using a degassing hollow fiber membrane described in JP-A-11-209670 have been tried. An apparatus incorporated in a printer has also been proposed in that ultrasonic degassing and hollow fiber membrane degassing can be performed continuously. Although not a physical method, Japanese Patent Application Laid-Open No. 11-263929 proposes a method for preventing bubble generation by a surfactant.

  Both methods are sufficiently effective with dissolved inks, but when using disperse dyes that are poorly soluble in water, it is difficult to prevent cavitation and achieve stable emission. is there.

  Furthermore, when incorporating in a printer, it is necessary to attach a deaeration device for each color ink, and space is required, so the printer becomes large and the cost increases. There is also a problem that the printer itself cannot be used in the event of failure. Further, when not used for a long time, there is a problem that aggregates are generated in the ink cartridge or in front of the deaeration device due to the gas contained in the ink.

In addition, it is described that the adsorbed air on the pigment surface is removed by using ultrasonic treatment and vacuum defoaming treatment in combination to strengthen the interaction with the dispersant and improve dispersibility (for example, Patent Document 2). But not for the purpose of improving cavitation.
JP-A-6-41878 Japanese Patent Laid-Open No. 9-286943

  An object of the present invention is to provide a method for producing an ink-jet ink and a recording method which are excellent in light-emitting properties and storage stability, and particularly suitable for ink-jet textile printing.

  As a result of intensive studies, the present inventors have found an ink-jet ink excellent in emission properties and storage stability. What is required of inkjet inks for textile printing in which disperse dyes are dispersed in fine particles is that dispersion stability is good, particle sedimentation does not occur, and nozzles and filters are not blocked. Probably, the adsorptivity of the dispersing agent to the coloring material has a great influence on the storage stability and stability of the dispersed ink.

  The inventor paid attention to the adsorption of the coloring material and the dispersant, and was able to obtain sufficient storage stability.

  In addition, if there are many impurities contained in the dye, clogging and sedimentation will occur, and the light emission will be affected. Furthermore, it is considered that the adsorbing power of the dispersant to the coloring material is also affected, and the storage stability is changed. When inorganic impurities are present, the value of electrical conductivity increases. Therefore, it is better that the color material has a smaller electrical conductivity.

  On the other hand, it is difficult to completely remove bubbles with the dispersed ink. Dissolved inks that use water-based dyes can be easily degassed by using a hollow fiber membrane module, but with dispersed inks that are used by dispersing solids in aqueous systems, the bubbles on the solid surface can be completely removed using the method described above. It can be difficult to remove. In that case, sufficient deaeration cannot be performed, and emission failure due to cavitation occurs. Although each of the deaeration operations already carried out and proposed has been independently examined, it has been difficult to achieve stable emission.

  Thus, as a result of studying various combinations, the present inventor has found that a detrimental effect can be obtained by performing deaeration with a combination of an ultrasonic wave and a hollow fiber membrane. Furthermore, it has been found that it is most effective to perform deaeration treatment first with a hollow fiber membrane and then with ultrasonic waves.

  Although the cause is not clear, it is considered as follows. First, degassing with a hollow fiber membrane removes gas dissolved in the ink and microbubbles (called bubble nuclei) present in the solvent. However, the surface of the disperse dye is not completely covered with the dispersant, and microbubbles are attached. Therefore, when vibration is applied by further irradiating ultrasonic waves, they are separated from the surface of the disperse dye and united to float on the gas-liquid interface or dissolve in the solvent, and the microbubbles disappear. Also, when the ultrasonic wave is irradiated first, even if the bubble nuclei are detached, it is difficult to dissolve because the gas is almost saturated in the ink, and it exists in the ink at the end of the ultrasonic irradiation. It is thought that the improvement effect is halved because the bubble nuclei that adhere are reattached.

  The present inventor can easily deaerate the ink by adjusting the moisture content and the electrical conductivity of the color material within a certain range without damaging the adsorption of the color material and the dispersant in the ink. I found a thing. That is, if the color material water content (and electrical conductivity) is high, the adsorbing sites on the color material surface are blocked, the dispersant cannot be adsorbed, the color materials are aggregated, and sedimentation occurs, resulting in a low color material water content. In addition, the color materials are strongly aggregated before being dispersed, and the dispersant cannot be sufficiently entangled on the surface of the color material, so that sedimentation occurs, resulting in poor emission and storage stability.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
A method for producing an ink-jet ink comprising using a color material having a water content of 0.01 to 10% by mass in a method for producing an ink-jet ink containing at least a color material, a dispersant, water and a water-soluble organic solvent. .
(Claim 2)
2. The method for producing an ink-jet ink according to claim 1, wherein an electrical conductivity is 0.1 to 10 mS / m when 5% by mass of the coloring material is mixed in water.
(Claim 3)
The method for producing an inkjet ink according to claim 1, wherein the colorant is a disperse dye.
(Claim 4)
In the manufacturing method of the inkjet ink of any one of Claims 1-3, the deaeration process by an ultrasonic wave and a hollow fiber membrane is performed to an inkjet ink before cartridge filling, The dissolved oxygen concentration of the inkjet ink after a process is made. A method for producing an ink-jet ink, characterized by comprising 2 ppm or less.
(Claim 5)
The method for producing an inkjet ink according to claim 4, wherein ultrasonic treatment is performed after deaeration treatment using a hollow fiber membrane.
(Claim 6)
An ink jet recording method using the ink manufactured by the method for manufacturing an ink jet ink according to claim 1.
(Claim 7)
The ink jet recording method according to claim 6, wherein an ink jet head having a nozzle diameter of 10 to 50 μm is used.
(Claim 8)
The inkjet recording method according to claim 6 or 7, wherein an inkjet head having a driving frequency of 8 kHz or more is used.

  By the production method and recording method of the present invention, it was possible to provide an ink having excellent emission properties and storage stability.

  Hereinafter, the present invention will be described in detail.

  As the coloring material of the present invention, known inorganic pigments, organic pigments, disperse dyes and the like can be used.

  Examples of organic pigments include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, and isoindolinone pigments. Inorganic pigments such as polycyclic pigments such as quinophthalone pigments, dye lakes such as basic dye type lakes, acid dye type lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, etc. Examples thereof include carbon black.

  Specific organic pigments are exemplified below.

  Examples of pigments for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the orange or yellow pigment include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. And CI Pigment Yellow 138.

  Examples of pigments for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

  As the disperse dye that can be used in the present invention, various disperse dyes such as an azo disperse dye, a quinone disperse dye, an anthraquinone disperse dye, and a quinophthalone disperse dye can be used. Specific compound names are listed below, but the present invention is not limited thereto.

C. I. Disperse Yellow 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135, 140 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, 227 , 231,232
C. I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49 , 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139 142
C. I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328
C. I. Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69 77
C. I. Disperse Green9
C. I. Disperse Brown 1, 2, 4, 9, 13, 19
C. I. Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81 , 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 2 97, 301, 315, 330, 333
C. I. Disperse Black 1, 3, 10, 24 etc. are mentioned.

  The disperse dye content is preferably 3 to 20% by mass, more preferably 5 to 13% by mass.

  The disperse dye may be used as a commercial product, but it is preferable to carry out a purification treatment. As a purification method, a known recrystallization method, washing or the like can be used. The organic solvent used in the purification method and purification treatment is preferably selected as appropriate according to the type of dye.

  The moisture content and moisture content of the color material can be measured using, for example, a Karl Fischer titrator (capacitance titration moisture meter KF-06 manufactured by Mitsubishi Kasei Co., Ltd.). Using a microsyringe, 10 μl of pure water is precisely weighed, and the amount of moisture (mg) per ml of Karl Fischer reagent is calculated from the reagent titration required to remove this water. Next, 100-200 mg of the sample is precisely weighed and sufficiently dispersed in a measurement flask by a magnetic stirrer for 5 minutes. Thereafter, the measurement was started, the titer (ml) of the Karl Fischer reagent required for titration was determined, and the water content and water content were calculated from the following formula.

Water content (mg) = reagent consumption (ml) × reagent titer (mgH ₂ O / ml)
Water content (%) = (water content (mg) / sample amount (mg)) × 100
The moisture content is preferably 0.01 to 10% by mass, more preferably 0.5% by mass or less.

  Electrical conductivity can be measured as follows. In a beaker, ion-exchanged water and the sample are added and stirred so that the color material to be the sample becomes 5% by mass. After stirring, the beaker was immersed in an ultrasonic cleaner for 20 minutes and measured at 25 ° C. using a portable electric conductivity meter CM-14P manufactured by Toa Denpa Kogyo Co., Ltd. The electric conductivity is preferably 0.1 to 10 mS / m, more preferably 2 mS / m or less.

  Examples of the dispersant of the present invention include, for example, formalin condensate of sodium creosote oil sulfonate (eg, demole C), formalin condensate of sodium cresolsulfonate and sodium 2-naphthol-6-sulfonate, sodium cresolsulfonate. Formalin condensate, formalin condensate of sodium phenolsulfonate, formalin condensate of sodium β-naphtholsulfonate, formalin condensate of sodium β-naphthalenesulfonate (eg, demole N), sodium naphtholsulfonate, lignin Examples include sulfonates (for example, Vanillex RN), sodium paraffin sulfonate (for example, Efcol 214), copolymers of α-olefin and maleic anhydride (for example, Florene G-700), and the like. Sulfonic acid salts are preferred.

  As for the usage-amount of a dispersing agent, 20-200 mass% is preferable with respect to a coloring material. When the amount of the dispersant is small, the formation of fine particles and the dispersion stability are poor. These dispersants may be used alone or in combination.

  Depending on the structure of the color material used, foaming or gelation may occur during dispersion, resulting in poor fluidity. In addition to the ability to form fine particles and dispersion stability, foaming during dispersion and gelation of the dispersion It is necessary to select in consideration of the fluidity of the dispersion. An antifoaming agent may be added to improve foaming during dispersion. In addition, the dispersant affects the dyeability, dyeing rate, leveling, transferability, color tone, fastness, etc. of the fabric, and tarring of the dispersant or wetting agent when coloring at high temperatures. It is preferable to select in consideration of non-uniform dyeing due to the above.

  Since there is no dispersant that satisfies all of the above requirements, it is necessary to select an optimal dispersant according to the color material to be dispersed and to add an antifoaming agent or the like as necessary.

  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 (for example, N, N-dimethylformamide, etc.), heterocyclic rings (2-pyrrolidone etc.), acetonitrile And the like.

  The amount of the water-soluble organic solvent is preferably 10 to 60% by mass with respect to the total ink mass.

  The particle diameter of the color material is preferably 300 nm or less as the average particle diameter and 900 nm or less as the maximum particle diameter. This is because when the average particle size and the maximum particle size are large, clogging is likely to occur in an ink jet printing method in which light is emitted from a fine nozzle, and stable emission is not possible.

  The average particle size can be determined by a commercially available particle size measuring device using a light scattering method, an electrophoresis method, a laser Doppler method or the like. Specific examples of the particle diameter measuring apparatus include Zetar Sizer 1000 manufactured by Malvern. When measured by Malvern Zeta Sizer 1000, it can be said that there is no difference in the average particle diameter within ± 5% considering the measurement accuracy.

  Furthermore, an additive can be used for various performance improvement. As the additive, known antiseptics, antifungal agents, viscosity modifiers, metal chelating agents, antioxidants, ultraviolet absorbers and the like can be used. For the long-term storage stability of the ink, preservatives and antifungal agents may be added. As preservatives and antifungal agents, aromatic halogen compounds, methylene dithiocyanates, halogen-containing nitrogen sulfur compounds, 1,2- Examples include benzisothiazolin-3-one, but the present invention is not limited thereto.

Ink-jet ink is a dispersion device such as a ball mill, a sand mill, a roll mill, a speed line mill, a homomixer, or a sand grinder. Disperse dyes are dispersed in an aqueous dispersion medium at a high concentration, and the resulting dispersion is diluted 1 to 10 times. Furthermore, it can be manufactured by adding various additives into ink, degassing treatment and then filtering, and since there is no particular change in particle size before and after these degassing treatments, the emission is improved due to improved dispersibility. It is obvious that the cavitation at the time of ejection of the head is less likely to occur because the gas in the ink is sufficiently removed, and the stable emission is possible.

  As the hollow fiber membrane deaeration module used in the present invention, a commercially available one can be used. For example, Mitsubishi Rayon Co., Ltd. MHF series, Dainippon Ink & Chemicals, Inc. SEPAREL series, etc. are mentioned. The deaeration process using the hollow fiber membrane module is performed, for example, by supplying ink from the ink supply port at the end of the module to the inside of the hollow fiber membrane and sucking it from the gas deaeration port on the side wall of the module. Is reduced to 10 KPa or less, and dissolved gas in the ink that has passed through the membrane is discharged, and the degassed ink exits from the ink outlet at the other end of the module. In the deaeration process using this hollow fiber membrane module, ink can be supplied to the outside of the hollow fiber membrane and the inside can be decompressed.

Although the ultrasonic processing apparatus used for this invention is not specifically limited, Nippon Seiki Seisakusho Co., Ltd. circulation type RUS-600T (frequency 20kHz, maximum output 600W), Branson Co., Ltd. continuous type model 900 type (frequency 20kHz, Ultrasonic treatment conditions include frequency, amplitude, and irradiation energy. If the frequency is higher than 30 KHz, the cohesive action becomes stronger and the dispersibility deteriorates. Since the cavitation pressure is higher as the amplitude that is preferably performed in the range is larger, as a result of intensive studies that can be performed in a general amplitude range of 20 to 60 μm, the present inventors have an irradiation energy of 1 × 10 ⁴ to 1 × 10 ⁵ J in particular. And preferably 2 × 10 ⁴ to 8 × 10 ⁴ J. If the irradiation energy is too low, the ability to remove bubble nuclei is insufficient, and if it is too high, the temperature rises and causes aggregation. In addition, after the deaeration treatment, the ultrasonic treatment may be performed once stored in a kettle or the like, but it is preferable to perform the treatment continuously.

The dissolved air concentration can be obtained on the basis of the proportion of oxygen in the air by measuring the dissolved oxygen concentration. The dissolved oxygen concentration can be measured by the Ostwald method (Experimental Chemistry Course 1 Basic Operation [I], page 241, 1975, Maruzen), the mass spectrum method, or a simple galvanic cell type or polarographic type. It can be measured by an oxygen concentration meter or a colorimetric analysis method. The dissolved oxygen can be measured using a commercially available dissolved oxygen concentration meter (DO-30A type manufactured by Toa Denpa Kogyo Co., Ltd.). If the dissolved oxygen concentration exceeds 2 ppm, cavitation occurs during ink ejection, and it is preferably less than 1 ppm and more preferably 1 ppm or less. In order to obtain a high-definition image, an inkjet head having a nozzle diameter of 10 to 50 μm is used. It is preferable to record. 50 μm or less is preferable from the graininess, and 10 μm or more is preferable because the droplet volume becomes too small and is affected by airflow.

  The fabric used in the present invention is preferably a fabric mainly composed of polyester fibers. Fibers mainly composed of polyester fibers may be made into any form such as woven fabric, knitted fabric, and non-woven fabric. As the fabric, it is preferable that the polyester fiber is 100%, but a blended woven fabric or a blended non-woven fabric with rayon, silk, polyurethane, acrylic, nylon, wool, or the like can also be used. Further, the thickness of the yarn constituting the fabric as described above is preferably in the range of 10 to 100d.

  In the case of the ink jet textile printing method of the present invention, it is preferable to pre-treat the ink receiving layer for preventing image bleeding. As the pretreatment, a method in which 0.2 to 50% by mass of at least one substance such as a water-soluble polymer, a water-soluble metal salt, a polycation compound, a surfactant, and a water repellent can be used. It is preferable to use a method suitable for the fiber material.

As the water-soluble metal salt, inorganic salts such as alkali metals or alkaline earth metals such as KCl and CaCl ₂ , organic acid salts and the like can be used. As the polycation compound, polymers or oligomers of various quaternary ammonium salts, polyamine salts, and the like can be used. Some water-soluble metal salts and polycation compounds change the color tone of the dyed product or reduce the light fastness, and therefore are preferably selected according to the target dyed product.

  Examples of water-soluble polymers include natural polymers (for example, starches such as corn and wheat, cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, sodium alginate, guar gum, tamarind gum, locust bean gum, gum arabic, etc. Polysaccharides, proteins such as gelatin, casein, keratin, etc.) and synthetic polymers (for example, polyvinyl alcohol, polyvinyl pyrrolidone, acrylic acid polymers, etc.) can be used.

  As the surfactant, for example, anionic, cationic, amphoteric, and nonionic surfactants are used. Typically, anionic surfactants include higher alcohol sulfates, sulfonates of naphthalene derivatives, and the like. In addition, cationic surfactants include quaternary ammonium salts, amphoteric surfactants such as imidazolidine derivatives, and nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene propylene block polymer, sorbitan Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and ethylene oxide adducts of acetylene alcohol.

  Examples of the water repellent include silicon, fluorine-based and wax-based ones.

  These water-soluble polymers and surfactants that are preliminarily applied to the fabric are stable against high-temperature environments because they do not cause stains due to tarring and the like when ink-jet printing is performed and color is developed at high temperatures. It is preferable. Moreover, those water-soluble polymers and surfactants that are previously imparted to the fabric are preferably those that can be easily removed from the fabric by washing after ink jet printing and color development at high temperature.

  Moreover, a carrier can also be provided to the fabric from the viewpoint of dyeability. The compound used as a carrier is preferably a compound having characteristics such as large dyeing acceleration, simple use, stable, low burden on human body and environment, easy removal from fibers, and no influence on dye fastness. . Examples of the carrier include phenols such as o-phenylphenol, p-phenylphenol, methylnaphthalene, alkyl benzoate, alkyl salicylate, chlorobenzene and diphenyl, ethers, organic acids, hydrocarbons and the like. These promote the swelling and plasticization of fibers such as polyester, and have a function of making the disperse dye easily enter the fibers.

  In addition, a dyeing assistant can be added to the fabric. The dyeing assistant has the effect of reducing the amount of moisture that re-evaporates and shortening the temperature rising time by forming a eutectic compound with water aggregated on the fabric when steaming the printed fabric. Further, the eutectic compound has a function 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.

  The pretreatment agent is preferably selected according to the fabric material and fabric structure, and is preferably applied by a pad method, a coating method, a spray method or the like so as to contain 0.2 to 50% by mass in the fabric. In the textile printing method of the present invention, after forming an image by the ink jet recording method on the fabric containing the fiber that can be dyed with the disperse dye as described above (ink application) Step), the fabric to which the ink is applied is heat-treated (heat treatment step), and further, the fabric subjected to the heat treatment is washed (washing step), whereby the printing on the fabric is completed and a printed matter is obtained. In the textile printing method of the present invention, the disperse dye is fixed to the fiber by a method of heat-treating a fabric to which ink is applied. Further, as a method for removing unfixed dye from the fabric, a conventionally known cleaning method can be used, but it is particularly preferable to use a reduction cleaning.

  In the ink jet textile printing method for printing on a cloth, it is desirable to wind up the printed cloth after emitting the ink, develop a color by heating, and wash and dry the cloth. In ink jet textile printing, ink is printed on a fabric and simply left unattended, it does not dye well. In addition, when printing on a long fabric for a long time, the fabric comes out endlessly, and the printed fabric overlaps with the floor, etc., and it is unsafe and unexpectedly dirty. There is a case. Therefore, it is necessary to perform a winding operation after printing. During this operation, a medium not related to printing, such as paper, cloth, or vinyl, may be sandwiched between the cloths. However, it is not always necessary to wind up when cutting in the middle or short fabric.

  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. As the heat treatment method, a method suitable for the application, such as an oven, a heat roll, or steam, may be selected.

  Cleaning is necessary after 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, the fabric is dyed as well as a decrease in fastness. Therefore, cleaning according to the object to be removed and the purpose is necessary.

  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 addition, in the case of the inkjet printing method of the present invention, in order to obtain a uniform dyed product, natural impurities (oils, waxes, pectic substances, natural pigments, etc.) adhering to the fabric fibers before the ink receiving layer is pretreated on the fabric are obtained. ), It is desirable to wash away residues (such as glue) and dirt used in the fabric manufacturing process. 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.

  By this series of actions, the characteristics as ink for inkjet printing are utilized, and a fabric on which a beautiful pattern is printed is completed.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
[Preparation of Ink 1]
The following mixture was dispersed using a sand grinder. Dispersion stopped when the average particle size reached 200 nm. A dye having a water content of 4% by mass and an electric conductivity of 7 mS / m was used. The moisture content and electrical conductivity were determined by the methods described in the text.

<< Dispersion-1 >>
C. I. Disperse Yellow 149 25 parts Glycerin 25 parts Ion-exchanged water 25 parts Lignin sulfonate sodium (Vanilex RN Nippon Paper Industries Co., Ltd.) 25 parts Further mixed with the following ingredients, filtered with a 3 μm membrane filter and degassed. did.

Dispersion liquid-1 5.0 parts Ethylene glycol 40 parts Glycerin 15 parts Proxel GXL (S) (manufactured by Avicia Co., Ltd.) 0.01 part Florene G-700 (manufactured by Kyoei Chemical Co., Ltd.) 9 parts Ion-exchanged water Remaining florene G-700 was neutralized in advance using a required amount of sodium hydroxide. The prepared ink was deaerated by the following method and then vacuum-filled.

<Deaeration method-1>
The dispersion ink was deaerated at 10 kPa or less with a hollow fiber membrane module (SEPAREL PF-004D manufactured by Dainippon Ink and Chemicals, Inc.). Continuously, manufactured by Nippon Seiki Seisakusho Co., Ltd., ultrasonic homogenizer circulation type RUS-600T (frequency 20 kHz, output 600 W), irradiation energy 3.6 × 10 ⁴ J, (600 W for 1 minute / 1 L ink), flow rate 60 L 1 pass at / h.

(Measurement of dissolved oxygen concentration)
The ink before and after the deaeration treatment was sampled and measured at 25 ° C. and 1 atm using a dissolved oxygen concentration meter (DO-30A type manufactured by Toa Denpa Kogyo Co., Ltd.).

(Outgoing light evaluation 1)
Using a piezo-type head having a nozzle diameter of 50 μm, a driving frequency of 10 kHz, and the number of nozzles of 64, the emission was evaluated. The drive voltage was adjusted so that each ink volume was 60 pL. In an environment of 25 ° C. and a relative humidity of 50%, 500 ml of each ink was continuously discharged, and bending and non-occurrence that occurred until the ink ran out were evaluated according to the following evaluation criteria.

◎: All nozzle emission ○: Bending with 1 to 3 nozzles and missing shots Δ: Bending with 4 to 7 nozzles and missing shots ×: Bending with 8 to 12 nozzles and missing shots XX: Bending at 13 nozzles or more and missing.

(Outgoing light evaluation 2)
Using a piezo-type head having a nozzle diameter of 30 μm, a driving frequency of 20 kHz, and the number of nozzles of 64, the emission was performed and the emission performance was evaluated. The drive voltage was adjusted so that each ink volume was 20 pL. In an environment of 25 ° C. and a relative humidity of 50%, 500 ml of each ink was continuously discharged, and bending and non-occurrence that occurred until the ink ran out were evaluated according to the following evaluation criteria.

◎: All nozzle emission ○: Bending with 1 to 3 nozzles and missing shots Δ: Bending with 4 to 7 nozzles and missing shots ×: Bending with 8 to 12 nozzles and missing shots XX: Bending at 13 nozzles or more and missing.

(Outgoing evaluation 3 (storability evaluation))
The ink was filled in the cartridge and left at 40 ° C. for 2 weeks, and the evaluation was performed in the same manner as in the light emission evaluation 2.

<Process before and after fabric>
A 100% polyester fiber and a thread thickness of 50d was previously soaked in a pretreatment agent (polymer cation compound and guar gum), squeezed and dried. After printing, the fabric was heat-treated at 180 ° C. for 10 minutes, washed with water and dried.

(Preservation print graininess evaluation)
Gradation chart with halftone dot of 0% to 100% is printed with Konica Inkjet Printing Printer NassengerII KS-1600II, and then stored for 2 weeks at 40 ° C. Concentration was evaluated. A piezo head with a nozzle diameter of 30 μm was used for printing. Evaluation was performed according to the following criteria.

A: There is no roughness in the entire gradation before and after storage. O: There is no roughness before storage, but after storage, a slight roughness is felt in the low concentration region. X: There is a feeling of roughness both before and after storage.

(Filter property evaluation)
The prepared ink 2L was stored at 40 ° C. for 4 weeks, then passed through a metal mesh filter (# 3500 mesh, 10φ) to check for clogging, and the filter surface was observed with an electron microscope.

◎: No 2L clogging, no crystal growth observed by electron microscope ○: No 2L clogging, crystal growth observed by electron microscope Δ: Clogging occurred between 1 and 2L ×: Clogging occurred at 1L or less [ Preparation of ink 2]
A dispersion and an ink were prepared and evaluated in the same manner as the ink 1 except that the water content of the dye was 0.5% by mass and the electric conductivity was 2 mS / m.

[Preparation of Ink 3]
A dispersion and an ink were prepared and evaluated in the same manner as the ink 1 except that the water content of the dye was 0.5% by mass and the electrical conductivity was 1 mS / m.

[Preparation of Ink 4]
<Dispersion-2>
C. I. Pigment Yellow 74 95g
Demall C (Kao Corporation) 65g
Ethylene glycol 100g
Ion exchange water 120g
Were dispersed using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads to obtain a yellow pigment dispersion. The water content of the dye was 0.5% by mass and the electrical conductivity was 1 mS / m. The sediment was removed with a centrifuge.

Dispersion liquid-2 110 g
Nipol LX844B (manufactured by Nippon Zeon Co., Ltd .; solid content 40%) 50 g
200g ethylene glycol
150 g of propylene glycol
Olfin 1010 (Nisshin Chemical Co., Ltd.) 4g
Proxel GXL (Zeneca) 2g
Dioctyl sodium sulfosuccinate 0.1g
Sodium chloride 0.6g
These were finished to 1000 g with ion-exchanged water and sufficiently stirred, and then passed twice through a Millipore filter having a pore size of 1 micron to obtain an ink.

  The average particle size of the pigment was 122 nm. The particle size was measured using a Zetasizer 1000 manufactured by Malvern. The prepared ink was degassed in the same manner as ink 1 and then vacuum-filled for evaluation.

[Preparation of Ink 5]
A dispersion and an ink were prepared and evaluated in the same manner as the ink 3 except that the degassing method-1 was replaced with the degassing method-2.

<Deaeration method-2>
The dispersion ink was irradiated by an ultrasonic homogenizer circulation type RUS-600T (frequency 20 kHz, output 600 W) manufactured by Nippon Seiki Seisakusho Co., Ltd., irradiation energy 3.6 × 10 ⁴ J, (600 W for 1 minute / 1 L ink), flow rate 60 L 1 pass at / h. Subsequently, deaeration treatment was performed at 10 kPa or less with a hollow fiber membrane module (SEPAREL PF-004D manufactured by Dainippon Ink and Chemicals, Inc.).

[Preparation of Ink 6]
A dispersion and an ink were prepared and evaluated in the same manner as the ink 4 except that the degassing method-1 was replaced with the degassing method-2.

[Preparation of Ink 7]
A dispersion and an ink were prepared and evaluated in the same manner as in the preparation of Ink 1 except that a colorant having a moisture content of 11% by mass and an electrical conductivity of 11 mS / m was used.

[Preparation of Ink 8]
A dispersion and an ink were prepared and evaluated in the same manner as the ink 4 except that a colorant having a water content of 11% by mass and an electrical conductivity of 11 mS / m was used.

  From Table 1, the ink produced by the production method of the present invention is superior in emission properties as compared with the comparative ink, and clearly has excellent storage stability as judged from graininess and filter properties.

Claims (8)

A method for producing an ink-jet ink comprising using a color material having a water content of 0.01 to 10% by mass in a method for producing an ink-jet ink containing at least a color material, a dispersant, water and a water-soluble organic solvent. . 2. The method for producing an ink-jet ink according to claim 1, wherein an electrical conductivity is 0.1 to 10 mS / m when 5% by mass of the coloring material is mixed in water. The method for producing an inkjet ink according to claim 1, wherein the colorant is a disperse dye. In the manufacturing method of the inkjet ink of any one of Claims 1-3, the deaeration process by an ultrasonic wave and a hollow fiber membrane is performed to an inkjet ink before cartridge filling, The dissolved oxygen concentration of the inkjet ink after a process is made. A method for producing an ink-jet ink, characterized by comprising 2 ppm or less. The method for producing an inkjet ink according to claim 4, wherein ultrasonic treatment is performed after deaeration treatment using a hollow fiber membrane. An ink jet recording method using the ink manufactured by the method for manufacturing an ink jet ink according to claim 1. The ink jet recording method according to claim 6, wherein an ink jet head having a nozzle diameter of 10 to 50 μm is used. The inkjet recording method according to claim 6 or 7, wherein an inkjet head having a driving frequency of 8 kHz or more is used.