JP2005263836A - Inkjet-printing ink set, black ink for inkjet-printing and method for inkjet-printing by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet-printing ink set capable of obtaining a stable image irrespective to the change of heating time for color-developing of a printed cloth, also a black ink for inkjet-printing and a method for the inkjet-printing by using the same. <P>SOLUTION: This inkjet-printing ink set constituted by each of yellow, magenta, cyan or blue colored inkjet-printing inks containing at least a dispersion dyestuff, a dispersing agent, water and water-soluble organic solvent is characterized in that when each of the surface free energy of main dispersion dyestuffs contained in each of the inkjet-printing inks is plotted by taking each of non-polar components on a horizontal axis and each of the total values of the polar components and hydrogen bonding components on a vertical axis, the maximum value of the distance between those of each of the dispersion dyestuffs is ≤8 mN/m. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel inkjet printing ink set for inkjet printing, a black ink for inkjet printing, and an inkjet printing method using the same.

  An ink jet image printing method is a method in which fine droplets of ink are ejected from an ink jet recording head and attached to a target recording medium for printing. The ink jet method is advantageous in that its mechanism is relatively simple, inexpensive, and can form a high-definition and high-quality image.

  Taking advantage of this ink jet system, development is also progressing on image printing on fabric, so-called ink jet textile printing. Unlike conventional textile printing, ink jet textile printing has the advantage that it is not necessary to prepare a plate and can quickly form an image with excellent gradation. Further, since only a necessary amount of ink is used as a formed image, it can be said that this is an excellent image forming method having environmental advantages such as less waste liquid compared to the conventional method.

  In ink jet textile printing, the types of dyes that can be used are limited by the types of fibers constituting the fabric, and disperse dyes are generally used for dyeing fibers such as polyester.

  When disperse dyes are used for ink jet printing inks, in addition to the performance of color tone and fastness, which are the criteria for conventional dye selection for ink jet printing, the ink jet recording method uses fine nozzles to discharge fine particles. It is necessary to satisfy requirements such as dispersibility for forming particles, prevention of nozzle clogging, and dispersion stability, and there are many restrictions on dye selection. In particular, an ink using a disperse dye as a colorant is a dispersion system in which fine particles of colorant are dispersed in an aqueous medium, so that coarse particles are likely to be generated as compared with a dissolved ink that is a complete solution. In addition, performance such as clogging or sedimentation during storage over a long period of time due to generation of coarse particles due to aggregation during production or ink storage is required.

  In textile printing using disperse dyes, color development is usually performed. Moreover, in the inkjet textile printing with respect to a fabric, pre-processing is normally performed. At this time, the color of the final print after coloring is affected by the degree of drying after printing on the pretreated fabric.

  For this reason, as a method for suppressing quality fluctuations in the color development process, an ink jet recording method is disclosed in which the printing order of ink jet textile ink is defined and a stable black image is created with an acid dye (see, for example, Patent Document 1). . In addition, a method for obtaining a stable image with respect to a change in conditions with respect to heating by defining a use ratio of a cyan dye and a blue dye using a disperse dye is disclosed (see, for example, Patent Document 2).

However, it has been found that the method disclosed in the above-mentioned patent document cannot obtain a sufficiently stable color against the variation of the heating time for the pretreated cloth.
JP-A-6-57651 JP-A-8-35181

  SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its object is to provide an ink jet printing ink set, a black ink for ink jet printing, and an ink jet using the same, which can obtain a stable image with respect to fluctuations in the heating color development time of the print cloth. Provide a printing method.

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

(Claim 1)
The surface of the main disperse dye contained in the ink jet printing ink set in the ink jet printing ink set comprising yellow, magenta and cyan or blue ink jet printing inks containing at least a disperse dye, a dispersant, water and a water-soluble organic solvent When the free energy is plotted on the horizontal axis for each nonpolar component and the total value of the polar component and the hydrogen bond component on the vertical axis, the maximum distance between the disperse dyes is 8 mN / m or less. Inkjet textile printing ink set characterized by

(Claim 2)
The ink-jet printing ink set according to claim 1, wherein the maximum distance between the disperse dyes is 6 mN / m or less.

(Claim 3)
The ink-jet printing ink set according to claim 1, wherein the maximum distance between the disperse dyes is 4 mN / m or less.

(Claim 4)
In a black ink for inkjet printing containing at least a plurality of disperse dyes, a dispersant, water, and a water-soluble organic solvent, the surface free energy of the plurality of disperse dyes is represented by a polar component and hydrogen with each nonpolar component as a horizontal axis. A black ink for inkjet printing, wherein the maximum value of the distance between each disperse dye is 8 mN / m or less when the total value with the binding component is plotted on the vertical axis.

(Claim 5)
5. The black ink for inkjet printing according to claim 4, wherein the maximum distance between the disperse dyes is 6 mN / m or less.

(Claim 6)
5. The black ink for inkjet printing according to claim 4, wherein the maximum distance between the disperse dyes is 4 mN / m or less.

(Claim 7)
An inkjet textile printing method for recording an image by ejecting the inkjet textile ink constituting the inkjet textile ink set according to any one of claims 1 to 3 from a recording head, wherein the nozzle diameter of the recording head is 30 μm or less. An ink-jet printing method comprising:

(Claim 8)
In the inkjet textile printing method which records an image by discharging the inkjet textile ink which constitutes the inkjet textile ink set according to any one of claims 1 to 3 from a recording head, the drive frequency of the recording head is 20 kHz or more An inkjet printing method characterized by the above.

(Claim 9)
An inkjet printing method for recording an image by discharging the inkjet printing ink constituting the inkjet printing ink set according to any one of claims 1 to 3 from a recording head, and discharging speed of the inkjet printing ink of the recording head Is 6 m / s or more.

(Claim 10)
An inkjet textile printing method for recording an image by ejecting the black ink for inkjet textile printing according to any one of claims 4 to 6 from a recording head, wherein the nozzle diameter of the recording head is 30 μm or less. Inkjet printing method.

(Claim 11)
An ink jet textile printing method for recording an image by ejecting the black ink for ink jet textile printing according to any one of claims 4 to 6 from a recording head, wherein a driving frequency of the recording head is 20 kHz or more. Inkjet printing method.

(Claim 12)
An inkjet printing method for recording an image by discharging the black ink for inkjet textile printing according to any one of claims 4 to 6 from a recording head, wherein the ejection speed of the black ink for inkjet textile printing of the recording head is 6 m. / S or more, The inkjet textile printing method characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the inkjet printing ink set which can obtain a stable image with respect to the fluctuation | variation of the heating color development time of a print cloth, the black ink for inkjet printing, and the inkjet printing method using the same can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor has determined that each of yellow, magenta, cyan, and blue inkjet printing inks (hereinafter simply referred to as inks) containing at least a disperse dye, a dispersant, water, and a water-soluble organic solvent. When the surface free energy of the main disperse dye contained in the inkjet textile printing ink is plotted on the horizontal axis for each nonpolar component and the total value of the polar component and the hydrogen bonding component on the vertical axis, Ink-jet textile printing ink set (hereinafter also simply referred to as ink set) having a maximum distance between each disperse dye of 8 mN / m or less, or contains at least a plurality of disperse dyes, a dispersant, water and a water-soluble organic solvent. The surface free energy of the plurality of disperse dyes is the sum of the polar component and the hydrogen bond component on the horizontal axis of each nonpolar component. When the image is recorded using a black ink for inkjet textile printing (hereinafter also simply referred to as black ink) having a maximum distance between the disperse dyes of 8 mN / m or less when plotted in FIG. As soon as it has been found that a stable image can be obtained with respect to time fluctuations, the present invention has been achieved.

  In other words, in an inkjet ink in which a disperse dye is dispersed in water as a colorant, the surface free energy of the disperse dye is found to have a great influence, and the relationship between the components of the surface free energy is close for multiple types of disperse dyes. It has been found that by selecting a disperse dye, it is possible to greatly improve the stability of the pretreatment conditions, particularly the heating time.

  The detailed mechanism that can greatly improve the stability with respect to the heating time by the configuration defined in the present invention is not clear at this stage, but is presumed as follows.

  That is, it is considered that the color stability due to the difference in the amount of the pretreatment agent is influenced by the moving speed of the dye in the pretreatment agent and the penetration rate into the fiber during color development.

  In such a situation, by designating and limiting the surface free energy difference between the dyes within a certain range as each dye to be used, the moving speed to the pretreatment agent glue and fiber is designed to be equal. It is considered that color variation due to color development conditions could be suppressed. In the black image, because of the visual nature of the human eye, it is very easy to feel the color difference, and in particular, a mixed color image composed of a mixture of colors and a plurality of dyes such as a yellow dye, a magenta dye, and a cyan or blue dye. In the black ink configured as described above, the color variation appears remarkably. Further, although the reason is not clear, the improvement effect is particularly great at the time of high-speed printing by adopting the configuration defined in the present invention.

  Details of the present invention will be described below.

  In the ink set of the present invention, the surface free energy of the main disperse dyes contained in each of the inkjet printing inks of yellow, magenta and cyan or blue, respectively, the polar component and the hydrogen bonding component, with each nonpolar component as the horizontal axis The maximum value of the distance between the disperse dyes is 8 mN / m or less, preferably 6 mN / m or less, more preferably 4 mN / m or less. is there.

  Further, in the black ink for inkjet printing of the present invention, in the black ink for inkjet printing containing at least a plurality of disperse dyes, a dispersant, water and a water-soluble organic solvent, the surface free energy of the plurality of disperse dyes constituting the black ink When the non-polar component is plotted on the horizontal axis and the total value of the polar component and the hydrogen bonding component is plotted on the vertical axis, the maximum value of the distance between the disperse dyes is 8 mN / m or less. And preferably 6 mN / m or less, more preferably 4 mN / m or less.

  The surface free energy as used in the present invention is determined as a polar component, a nonpolar component, and a hydrogen bond component according to the Young-Fowkes equation.

  For example, the disperse dye to be measured is made into a tablet with a smooth surface using a tablet molding apparatus, and then the contact angle with respect to pure water, nitromethane, and diiodomethane is measured using a contact angle meter. Next, a polar component, a nonpolar component, and a hydrogen bond component are obtained as the surface energy of the object to be measured using the Young-Fowkes equation.

  In the present invention, an automatic / dynamic contact angle meter DCA-VZ manufactured by Kyowa Interface Science Co., Ltd. is used as the measuring device, and after measuring the contact angle to pure water, nitromethane, diiodomethane, a surface free energy analysis system Using the EG-25 type, the surface free energy was decomposed into three components, a nonpolar component, a polar component, and a hydrogen bonding component.

  The ink-jet printing ink set of the present invention is composed of yellow, magenta, cyan or blue ink-jet printing inks having different hues.

  In the ink according to the present invention constituting the ink set of the present invention, the surface free energy of the main disperse dye contained in the disperse dye ink-jet printing ink is represented by the polar component, the hydrogen bond component, and the non-polar component on the horizontal axis. The maximum value of the distance between each disperse dye is 8 mN / m or less when the total value is plotted on the vertical axis. The main disperse dye in the present invention constitutes an ink jet textile ink. The disperse dye which occupies 50 mass% or more of the disperse dye to perform, Preferably it is 70 mass% or more, More preferably, it is 85 mass% or more, Most preferably, it is 95 mass% or more.

  By using the inkjet dye ink having the above-described configuration, the moving speed of each color ink in the paste can be designed to be equal, and a stable image free from color fluctuations with respect to changes in heating temperature can be obtained.

  The material constituting the fabric used in the inkjet printing method of the present invention is not particularly limited as long as it contains fibers that can be dyed with disperse dyes. Among them, fibers such as polyester, acetate, and triacetate are contained. Those are preferred. Among them, a fabric containing at least polyester fibers is particularly preferable. As the fabric, the above-described fibers may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Further, as the fabric that can be used in the present invention, it is preferable that the fiber that can be dyed with disperse dyes is 100%, but a mixed woven fabric with rayon, cotton, polyurethane, acrylic, nylon, wool, silk, etc. Alternatively, a blended nonwoven fabric or the like can also be used as a textile for printing. 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 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 fiber before pretreatment of the fabric with water-soluble polymers ), It is desirable to wash away residues (such as glue) and dirt of the chemical used in the fabric manufacturing process. Examples of the cleaning agent used for cleaning include alkalis such as sodium hydroxide and sodium carbonate, surfactants such as anionic surfactants and nonionic surfactants, enzymes, and the like.

  In the inkjet textile printing method of the present invention, it is preferable to apply a pretreatment agent by a pad method, a coating method, a spray method or the like (pretreatment step) in order to prevent bleeding. 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.

  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.

  Specific water-soluble polymers used for the pretreatment include, for example, starches such as corn and wheat, cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, sodium alginate, and guar gum. Polysaccharides such as tamarind gum, locust bean gum and gum arabic, protein substances such as gelatin, casein and keratin, and synthetic water-soluble polymers include, for example, polyvinyl alcohol, polyvinyl pyrrolidone and acrylic acid polymers. it can.

  As the surfactant, for example, anionic, cationic, amphoteric, and nonionic surfactants are used. Typically, anionic surfactants include higher alcohol sulfates and sulfonates of naphthalene derivatives. Quaternary ammonium salt and the like as ionic surfactant; imidazoline derivative and the like as amphoteric surfactant; polyoxyethylene alkyl ether and polyoxyethylene propylene block polymer as nonionic surfactant Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, ethylene oxide adduct of acetylene alcohol, and the like.

  Examples of the water repellent include silicon, fluorine-based and wax-based ones. These water-soluble polymers and surfactants that are pre-applied to the fabric are stable against high-temperature environments because they do not cause dirt due to taring when ink-jet printing and color development at high temperatures. Preferably there is. Further, these 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.

  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 not printed well just by printing it on a cloth and leaving it alone. In addition, when printing on a long fabric for a long time, the fabric comes out endlessly, and the printed fabric overlaps the floor etc., leaving a place that 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 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.

  When dyeing with a disperse dye, a carrier may be used in addition to a method of coloring at a high temperature. The compound used as the 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 the fiber, and no influence on dye fastness. Examples of carriers include o-phenylphenol, p-phenylphenol, methylnaphthalene, alkyl benzoate, alkyl salicylate, phenols such as chlorobenzene and diphenyl, ethers, organic acids, hydrocarbons and the like. These promote the swelling and plasticization of difficult-to-dye fibers that are difficult to dye at temperatures around 100 ° C. like polyester, and make it easier for disperse dyes to enter the fibers. The carrier may be preliminarily adsorbed on the fibers of the fabric used for inkjet printing, or may be included in the inkjet ink.

  After the heat treatment, a cleaning process is necessary. 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.

  A disperse dye is used as the coloring material in the present invention. Disperse dyes are nonionic dyes that do not have ionic water-soluble groups such as sulfonic acid and carboxy groups, and have a low solubility in water. Used for staining. Unlike pigments, it is soluble in organic solvents such as acetone and dimethylformamide. Moreover, it is possible to diffuse and color in a synthetic fiber in a molecular form.

  The present invention relates to a disperse dye, but in order to dye a fabric composed of a plurality of types of fibers by blending, union or the like, a color material other than the disperse dye, such as an acid dye or a direct dye, is mixed and used. It is also possible.

  Specific compounds of preferred disperse dyes in the present invention are shown below. However, it is not limited to the compound illustrated to these.

[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, 23 , 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 Green]
9,
[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, 297, 301, 315, 3 0,333,
[C. I. Disperse Black]
1, 3, 10, 24,
Etc.

  In ink-jet textile printing using disperse dyes, when coloring at high temperature processing, it is possible to select disperse dyes with good sublimation fastness because they do not cause contamination due to dye sublimation on the white background of machines and fabrics. preferable.

  As content of a disperse dye, 0.1-20 mass% is preferable, and 0.2-13 mass% is more preferable. 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.

  Examples of the water-soluble organic solvent according to 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.), amino (Eg, 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, Ethylene 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.

  An inorganic salt may be added to the ink in order to improve the color development in order to keep the ink viscosity and dye stable. Examples of inorganic salts include sodium chloride, sodium sulfate, magnesium chloride, magnesium sulfide and the like. When implementing this invention, it is not limited to these.

  As the surfactant, any of cationic, anionic, amphoteric and nonionic can be used. Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Examples of anionic surfactants include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, alkyl ether carboxylate, acylated peptide , Alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate Salts, secondary higher alcohol sulfates, alkyl ether sulfates, secondary higher alcohol ethoxy sulfates, polyoxyethylene alkylphenyl ether sulfates, monoglyculates, fatty acid alkylolamide sulfates, alkyl ether phosphates Salt, alkyl phosphate ester salt and the like. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether (eg, Emulgen 911), polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxy Ethylene polyoxypropylene alkyl ether (for example, Newpol PE-62), polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters , Sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkyl amine oxides, acetylene glycol, acetylene alcohol, and the like. The present invention is not limited to these.

  When these surfactants are used, they can be used singly or as a mixture of two or more kinds. By adding 0.001 to 1.0% by mass with respect to the total amount of ink, the surface of the ink can be used. The tension can be arbitrarily adjusted, which is preferable.

  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, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL), and the like. It is done. The present invention is not limited to these.

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

  The particle size of the disperse dye is preferably 300 nm or less as the average particle size and 900 nm or less as the maximum particle size. 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 diameter can be determined by a commercially available particle size measuring instrument 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.

  Dispersants preferably used in the present invention include, for example, a formalin condensate of sodium creosote oil sulfonate (eg, demole C), a formalin condensate of sodium cresol sulfonate and sodium 2-naphthol-6-sulfonate, and cresol sulfone. Formalin condensate of sodium sulfonate, formalin condensate of sodium phenol sulfonate, formalin condensate of sodium β-naphthol sulfonate, formalin condensate of sodium β-naphthalene sulfonate (eg, demole N) and sodium β-naphthol sulfonate , Lignin sulfonate (for example, Vanillex RN), sodium paraffin sulfonate (for example, Efcol 214), a copolymer of α-olefin and maleic anhydride (for example, Florene G-700), and the like. It is.

  As for the usage-amount of a dispersing agent, 20-200 mass% is preferable with respect to a disperse dye. When the amount of the dispersant is small, the formation of fine particles and the dispersion stability is poor, and when the amount of the dispersant is large, the formation of fine particles and the dispersion stability is deteriorated and the viscosity becomes high. These dispersants may be used alone or in combination.

  Preferred wetting agents for dispersion according to the present invention are sodium dodecylbenzenesulfonate, sodium 2-ethylhexylsulfosuccinate, sodium alkylnaphthalenesulfonate, ethylene oxide adduct of phenol, ethylene oxide adduct of acetylenediol, and the like. .

  Depending on the structure of the disperse dye used, foaming, gelation, and fluidity may be deteriorated during dispersion. Dispersants and wetting agents are not limited to wetting ability, atomization ability, and dispersion stability. It is necessary to select in consideration of foaming during dispersion, gelation of the dispersion, fluidity of the dispersion, and the like. Dispersants and wetting agents affect the dyeability, dyeing rate, leveling, transferability, color tone, fastness, etc. of the fabric, and when developing at high temperatures, It is preferable to select in consideration of non-uniform dyeing due to tarring of the agent. Since there is no dispersant that satisfies all of the above requirements, it is necessary to select an optimal dispersant according to the dye to be dispersed and add an antifoaming agent or the like as necessary.

  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.

  The dissolved oxygen can be determined by measuring at 25 ° C. and 101 kPa using a commercially available dissolved oxygen concentration meter, for example, DO-30A type manufactured by Toa Denpa Kogyo Co., Ltd.

  The recording head used in the ink jet textile printing method of the present invention is not particularly limited, and either a thermal type or a piezo type can be used.

  In the present invention, in order to obtain a high-definition image, recording is preferably performed using an inkjet head having a nozzle diameter of 30 μm or less. In order to improve the granularity, the smaller one is preferable, but since the droplet volume becomes too small and is influenced by the air flow, the range of 10 to 20 μm is particularly preferable.

  The drive frequency of the ink jet head drive device is preferably 20 kHz or more, and more preferably 30 kHz or more and 100 kHz or less in order to prevent ink clogging. For the same reason, the ink discharge speed is preferably 6 m / s or more, more preferably 8 m / s or more and 50 m / s or less.

  In the ink jet textile printing method of the present invention, the volume of droplets when flying ink is preferably 5 pl or more from the viewpoint of being less susceptible to the influence of the air current in the vicinity of the recording head, and 150 pl or less from the viewpoint of graininess of the printed image. Is preferable, and more preferably 5 to 80 pl.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
<Preparation of dye dispersion>
The following compositions were dispersed using a sand grinder to prepare dye dispersions Y1, Y2, M1, M2, C1, C2, and C3. Dispersion stopped when the average particle size reached 200 nm.

Disperse dye (disperse dye species listed in Table 1) 25 parts Glycerin 25 parts Ion-exchanged water 25 parts Dispersant A (Sodium lignin sulfonate, Vanillex RN, manufactured by Nippon Paper Industries Co., Ltd.)
12 parts Dispersant B (Floren G-700, manufactured by Kyoeisha Chemical Co., Ltd.) 3 parts << Preparation of ink >>
The following compositions are added to and mixed with each of the dye dispersions prepared above, and filtered and degassed with a 3 μm membrane filter to prepare inks Y1, Y2, M1, M2, C1, C2, and C3. did.

Dye dispersion (dye dispersion described in Table 1) 40 parts Ethylene glycol 40 parts Diethylhexyl sulfosuccinate sodium 0.1 part Proxel GXL (S) (manufactured by Avicia Co., Ltd.) 0.1 part Finally, ion-exchanged water is added 100 parts.

  In addition, each ink prepared according to the above method is prepared by passing the ink through a gas permeable hollow fiber membrane (manufactured by Mitsubishi Rayon) and reducing the pressure on the outer surface side of the hollow fiber membrane with a water aspirator. The dissolved gas inside was removed. After degassing, these inks were filled into vacuum packs to prevent air from entering.

  In addition, the non-polar component, the polar component, and the hydrogen bond component which are the surface energy components of each dye described in Table 1 are pure water using an automatic / dynamic contact angle meter DCA-VZ type manufactured by Kyowa Interface Science Co., Ltd. After measuring the contact angle with respect to nitromethane and diiodomethane, the surface free energy was determined by decomposing it into three components, a nonpolar component, a polar component, and a hydrogen bond component, using a surface free energy analysis system EG-25.

  Then

<< Image formation and evaluation >>
[Preparation of ink set]
Ink sets A, B, C, and D were prepared by configuring the inks prepared as described above in combinations shown in Table 2.

  For the dyes used in the inks constituting each ink set, the combination of the dyes that are the farthest away in the surface free energy plot was determined, and the distance difference (mN / m) was measured.

[Preparation of Print 1]
Each of the ink sets A, B, C, and D prepared above is loaded into a Nassenger-II manufactured by Konica Minolta Technology Center, and an evaluation image is placed on a pretreated A cloth (polyester) manufactured by Konica Minolta Technology Center. Printed on.

  The evaluation image is a three-color mixed image in which each color of yellow, magenta, and cyan is output in the same area by 50% at 300 dpi.times.300 dpi, assuming that 100% is a single color when all are landed at 300 dpi.times.300 dpi. Images were used. In the present invention, dpi represents the number of dots per 2.54 cm.

[Preparation of Print 2]
Instead of the Nassenger-II manufactured by Konica Minolta Technology Center Co., Ltd. used for the production of the printed matter 1, four piezo heads having a driving frequency of 20 kHz and a nozzle diameter of 30 μm were used, and the droplet speed of each color was 6 m / s. Using a printer equipped with a head unit adjusted as described above, each was loaded into a Knit Minolta Technology Center Nassenger-II and the evaluation image was placed on a pre-treated A cloth (polyester) manufactured by Konica Minolta Technology Center. Printed.

  As the evaluation image, a three-color mixed image in which each color of yellow, magenta, and cyan is output by 50% in the same area at 750 dpi × 750 dpi was used.

[Heat treatment of printed matter]
Each of the produced printed materials was dried at room temperature for 12 hours, and then heated and colored at 195 ° C. for 18 minutes, 20 minutes, and 22 minutes, respectively. After color development, after reducing and washing and drying naturally, using a Macbeth densitometer (X-rite 938), L ^* , a ^* , b ^* are measured, and the printed material is heated for 20 minutes and heated for 18 minutes. The color difference ΔE1 from the treated printed material was measured according to the following formula.

ΔE1 = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
In the same manner as described above, the color difference ΔE2 between the printed material subjected to the heat treatment for 20 minutes and the printed material subjected to the heat treatment for 22 minutes was measured according to the above formula, and the obtained results are shown in Table 2.

  As can be seen from the results shown in Table 2, the ink set of the present invention comprising a combination in which the maximum value of the surface free energy difference of the disperse dyes contained in each color inkjet printing ink is 8 mN / m or less is formed. It can be seen that the color difference variation of the obtained image is small with respect to the variation of the heating time during color development.

Example 2
<Preparation of black ink>
Using the dye dispersions prepared in Example 1 in combinations shown in Table 3, black inks A, B, C, and D having the following constitutions were prepared.

  In addition, each black ink prepared according to the above method, by passing the ink through a gas-permeable hollow fiber membrane (manufactured by Mitsubishi Rayon), and decompressing the outer surface side of the hollow fiber membrane with a water flow aspirator, The dissolved gas in the ink was removed. After degassing, these black inks were filled into a vacuum pack to prevent air from entering.

Yellow dye dispersion (dispersion types are listed in Table 3) 20 parts Magenta dye dispersion (dispersion types are listed in Table 3) 20 parts Cyan dye dispersion (dispersion types are listed in Table 3) 20 Part Ethylene glycol 20 parts Diethylhexyl sulfosuccinate sodium 0.1 part Proxel GXL (S) (manufactured by Avicia Co., Ltd.) 0.1 part Finally, ion exchange water was added to make 100 parts.

<< Image formation and evaluation >>
Using the black inks A to D prepared above, each printed matter was prepared in the same manner as the printed matter 1 and the printed matter 2 in the same manner as in the method described in the first example. According to the method, the color difference due to the color development heating time change of the printed matter was measured, and the obtained results are shown in Table 3.

  As is apparent from the results shown in Table 3, an image formed using the black ink for ink-jet printing of the present invention in which the maximum value of the surface free energy difference among a plurality of disperse dyes is 8 mN / m or less is It can be seen that the variation in color difference is small with respect to the variation in heating time.

Claims (12)

The surface of the main disperse dye contained in the ink-jet printing ink set in the ink-jet printing ink set comprising yellow, magenta, and cyan or blue ink-jet printing inks containing at least a disperse dye, a dispersant, water and a water-soluble organic solvent When the free energy is plotted on the horizontal axis for each nonpolar component and the total value of the polar component and the hydrogen bond component on the vertical axis, the maximum distance between the disperse dyes is 8 mN / m or less. Inkjet textile printing ink set characterized by The ink-jet printing ink set according to claim 1, wherein the maximum distance between the disperse dyes is 6 mN / m or less. The ink-jet printing ink set according to claim 1, wherein the maximum distance between the disperse dyes is 4 mN / m or less. In a black ink for inkjet printing containing at least a plurality of disperse dyes, a dispersant, water, and a water-soluble organic solvent, the surface free energy of the plurality of disperse dyes is represented by a polar component and hydrogen with each nonpolar component as a horizontal axis. A black ink for inkjet printing, wherein the maximum value of the distance between each disperse dye is 8 mN / m or less when the total value with the binding component is plotted on the vertical axis. 5. The black ink for inkjet printing according to claim 4, wherein the maximum distance between the disperse dyes is 6 mN / m or less. 5. The black ink for inkjet printing according to claim 4, wherein the maximum distance between the disperse dyes is 4 mN / m or less. An inkjet textile printing method for recording an image by ejecting the inkjet textile ink constituting the inkjet textile ink set according to any one of claims 1 to 3 from a recording head, wherein the nozzle diameter of the recording head is 30 μm or less. An ink-jet printing method comprising: In the inkjet textile printing method which records an image by discharging the inkjet textile ink which constitutes the inkjet textile ink set according to any one of claims 1 to 3 from a recording head, the drive frequency of the recording head is 20 kHz or more An inkjet printing method characterized by the above. An inkjet printing method for recording an image by discharging the inkjet printing ink constituting the inkjet printing ink set according to any one of claims 1 to 3 from a recording head, and discharging speed of the inkjet printing ink of the recording head Is 6 m / s or more. An inkjet textile printing method for recording an image by ejecting the black ink for inkjet textile printing according to any one of claims 4 to 6 from a recording head, wherein the nozzle diameter of the recording head is 30 μm or less. Inkjet printing method. An ink jet textile printing method for recording an image by ejecting the black ink for ink jet textile printing according to any one of claims 4 to 6 from a recording head, wherein a driving frequency of the recording head is 20 kHz or more. Inkjet printing method. An inkjet printing method for recording an image by discharging the black ink for inkjet textile printing according to any one of claims 4 to 6 from a recording head, wherein the ejection speed of the black ink for inkjet textile printing of the recording head is 6 m. / S or more, The inkjet textile printing method characterized by the above-mentioned.