JP6477064B2 - Water-based ink and inkjet printing method - Google Patents

Description

  The present invention relates to a water-based ink and an inkjet printing method.

  Fabric printing by the ink jet recording method (hereinafter also simply referred to as “inkjet printing”) is a process of ejecting ink from an ink jet head and landing on the fabric. The ink is contained by applying steam to the fabric on which the ink has landed. And fixing the dye to the fibers of the fabric, and washing the fabric to which the steam is applied to remove the unfixed dye.

  In ink jet textile printing, the type of ink is selected corresponding to the type of fabric forming the image. For example, in ink-jet printing on polyester fibers and other hydrophobic artificial fibers, an image is formed on a fabric with ink in which a disperse dye is dispersed in water.

  In inkjet printing, from the viewpoint of expanding the color gamut of an image to be formed, dyeing may be performed using an ink set in which inks of other colors are combined with inks of yellow, magenta, and cyan. At this time, a technique for developing a natural hue on a fabric by using an ink containing a plurality of disperse dyes having different hues as the other color ink is known.

For example, Patent Document 1 discloses that a natural hue of black can be developed at various densities from high density to low density. I. Disperse Blue (hereinafter simply referred to as “DB”) 60 or DB-165, C.I. I. Disperse Red (hereinafter simply referred to as “DR”) 92 or D R1 54, and C.I. I. Disperse Yellow (hereinafter simply referred to as “DY”) Inkjet printing inks containing 163 are disclosed.

JP 2014-177526 A JP 2014-224216 A

  In inkjet printing, in order to further enhance the appearance of the printed fabric, not only the surface of the fabric on which ink is landed (hereinafter simply referred to as “surface”) but also the surface of the opposite fabric (hereinafter simply referred to as “surface”). "Back side")) may be required to exhibit the same color tone. However, conventional inks sometimes do not have the same color tone on the front and back surfaces of the fabric.

  Also, when inkjet printing is performed using an ink containing disperse dyes of a plurality of colors, one or more disperse dyes may ooze out of the image from the edge of the part where the image is to be formed. Depending on the condition, the image may become unclear.

  In view of the above circumstances, the present invention is capable of developing the same color tone on both the front surface and the back surface of the ink for ink jet textile printing, and the disperse dye from the end of the portion where the image is to be formed. It is an object of the present invention to provide an ink that hardly causes bleeding and an ink jet textile printing method using such an ink.

The present invention relates to the following water-based ink for inkjet printing.
[1] A water-based ink for ink-jet printing containing water and a coloring material,
The coloring material includes a yellow disperse dye, a red disperse dye, a violet disperse dye, and a blue disperse dye,
The yellow disperse dye is C.I. I. Disperse Yellow 114,
The red disperse dye is C.I. I. Disperse Red 92, C.I. I. Disperse Red 152 and C.I. I. Disperse Red Including at least one selected from the group consisting of 191;
The violet disperse dye is C.I. I. Disperse Violet 57 and C.I. I. Disperse Violet Including one or both of 93,
The blue disperse dye is C.I. I. Disperse Blue 60,
The a * in the CIE L * a * b * color space obtained from the UV-visible absorption spectrum of the ink diluted 35-fold with water and 35-fold with acetone and then diluted 20-fold with acetone is 12 or more and 12 An aqueous ink, wherein b * is −32 or more and −20 or less.
[2] The violet disperse dye is C.I. I. Disperse Violet 57. The water-based ink according to [1], comprising 57.
[3] The red disperse dye is C.I. I. Disperse Red 92. The water-based ink according to [1] or [2], comprising 92.
[4] L * in the CIE L * a * b * color space obtained from an ultraviolet-visible absorption spectrum when the ink is diluted 700 times is 50 or more, [1] to [3] The water-based ink according to any one of the above.
[5] It further comprises at least one selected from the group consisting of a polyethylene glycol having a molecular weight of 400 or more and 1000 or less, a polypropylene glycol having a molecular weight of 400 or more and 1000 or less, and a compound represented by formula (1). , [1] to [4].

(In formula (1), R ₁₁ independently represents an ethylene glycol group or a propylene glycol group, and x, y, and z are all positive integers, and x + y + z = 3 to 30.)
[6] The water-based ink according to any one of [1] to [5], further containing an acrylic resin having an acid value of 150 mgKOH / g or less.

The present invention also relates to an inkjet printing method shown below.
[7] An ink-jet printing method comprising forming an image on a fabric with the water-based ink for ink-jet printing according to any one of [1] to [6].
[8] The inkjet textile printing method according to [7], wherein the fabric is a fabric in which an image forming portion includes a polyester fiber.

  According to the present invention, in ink for ink jet textile printing, the same color tone can be developed on both the front surface and the back surface, and disperse dye does not easily exude from the end of the portion where an image is to be formed. Inks and ink jet textile printing methods using such inks are provided.

FIG. 1 is a diagram schematically showing a part of the configuration of an ink jet printing apparatus capable of performing the image forming process of the ink jet textile printing method of the present invention.

1. Water-based ink for ink-jet printing The water-based ink for ink-jet printing according to the present invention (hereinafter also simply referred to as “the ink of the present invention”) contains water and a coloring material. The ink of the present invention contains a yellow disperse dye, a red disperse dye, a violet disperse dye, and a blue disperse dye as a colorant.

  The ink of the present invention develops a good color tone on the back side of the ink-jet printed fabric, thereby reducing the difference between the color tone of the front surface and the color tone of the back surface and hardly causing bleeding from the edge of the image. This is considered to be due to the following reasons.

  When steam is applied to the fabric landed with ink droplets, the movement of the polymer constituting the fiber of the fabric is activated by heat, and the fiber structure of the polyester in which the hydrophobic disperse dye dissolved in the high-temperature steam is the hydrophobic fabric Easy to penetrate. In this way, the disperse dye penetrates into the fiber structure and is fixed, whereby the fabric is colored. When the disperse dye contained in the ink droplets penetrates into the fiber structure, the disperse dye travels along the surface of the fiber structure of the fabric and diffuses from the front surface to the back surface. However, disperse dyes that are difficult to dissolve in vapor are highly hydrophobic and therefore are more easily distributed to the fiber structure than vapor, and are more likely to penetrate and fix in the fiber structure, making it difficult to reach the back of the fabric. Conversely, disperse dyes that are easily dissolved in vapor are less hydrophobic and therefore are more easily distributed to the vapor than the fiber structure, and are less likely to penetrate into the fiber structure, and therefore easily reach the back of the fabric. For this reason, if there is a difference in solubility in vapor among disperse dyes, the color of disperse dyes that are difficult to diffuse to the back side (hard to dissolve in vapor) on the back side of the fabric easily diffuses to the back side (dissolves in vapor). The difference between the color tone of the surface of the fabric and the color tone of the back surface is increased because it is less likely to develop than the color tone of the disperse dye.

  In addition, disperse dyes that are easily dissolved in vapor are not easily fixed by penetrating into the fiber structure, and are easily diffused along the surface of the fiber, so that they are easily diffused to the outside of the image end and cause bleeding at the image end.

  If the ink contains a disperse dye that is too soluble in vapor, the disperse dye having a high solubility dissolves in the water in the ink, and promotes crystal growth of other disperse dyes that are not dissolved. Large volume particles may be formed (Ostwald growth). When such a large volume of particles is formed, the ink ejectability from the ejection nozzle may be lowered. On the other hand, disperse dyes with too low solubility have low solubility in water at room temperature, and thus precipitate and aggregate during storage of the ink, which may reduce the storage and ejection properties of the ink.

  Therefore, by combining disperse dyes that have a small difference in solubility in vapor and that are not too high or too low, the difference between the color tone of the surface of the fabric and the color tone of the back surface is small. It is possible to obtain an ink which hardly causes bleeding at the end portion and has high ink ejection stability.

  By measuring the coordinate values in the CIE L * a * b * color space from the ultraviolet-visible absorption spectrum of the ink, it is possible to infer what color the image printed with the ink will exhibit. From the viewpoint of exhibiting a clear color when inkjet printing is performed, the dye is obtained by diluting the ink 35 times with water and then measuring the ink diluted with acetone 20 times with an ultraviolet spectrum measuring instrument. In the CIE L * a * b * color space, a * is −12 or more and 12 or less, and b * is −32 or more and −20 or less.

  From the viewpoint of forming a more neutral gray image, L * is preferably 50 or more and 80 or less in the CIE L * a * b * color space, and from the above viewpoint, it is 50 or more and 65 or less. Is more preferable.

  Hereinafter, the ink of the present invention will be described in more detail through detailed description of each component.

1-1. Color Material The color material includes a yellow disperse dye, a red disperse dye, a violet disperse dye, and a blue disperse dye. From the standpoint of adjusting the color tone to a desired range, the colorant has a coordinate value a * of the ink of the present invention in the CIE L * a * b * color space of −12 to 12, and b * of −32 to −20. Thus, other disperse dyes may be included as long as the ink capable of producing the effects of the present invention can be prepared. In the present invention, the disperse dye is specified by a color index name registered in a color index (ColorIndex) which is a database jointly created by the British Dye Dyeing Society and the American Textile Chemical Technology and Dyeing Technology Association. .

  From the viewpoint of improving color development, the content of the coloring material is preferably 0.5% by mass or more and 5.5% by mass or less with respect to the total mass of the ink. From the viewpoint of further clarifying the color tone produced by the ink of the present invention, the content of the coloring material is more preferably 2.0% by mass or more and 3.5% by mass or less with respect to the total mass of the ink. preferable.

1-1-1. Yellow Disperse Dye The yellow disperse dye contains DY1 14.

  The yellow disperse dye may be contained in the ink together with other disperse dyes so long as the desired color tone can be obtained. For example, 0.1 mass with respect to the total mass of the ink of the present invention. % Or more and 1.0% by mass or less is preferable.

1-1-2. Red-based disperse dye The red-based disperse dye includes at least one selected from D R92 , D R1 52, and D R1 91. Of these, DR92 is preferred from the viewpoint of making the difference between the color tone of the surface of the fabric and the color tone of the back surface less likely to cause bleeding at the edge of the image.

  The red disperse dye may be contained in the ink together with other disperse dyes so long as a desired color tone can be obtained. For example, 0.1% by mass with respect to the total mass of the ink of the present invention. % Or more and 1.2% by mass or less is preferable.

1-1-3. Violet disperse dyes Violet disperse dyes include C.I. I. Disperse Violet (hereinafter simply referred to as “DV”) 57 or D V93 . Among these, D V57 is preferable from the viewpoint of reducing the difference between the color tone of the surface of the fabric and the color tone of the back surface. Further, from the viewpoint of making the difference between the color tone of the surface of the fabric and the color tone of the back surface smaller and making it difficult to cause bleeding at the edge of the image, the violet disperse dye is D V57 , and the red The disperse dye is preferably DR92 .

  The content of the violet disperse dye may be an amount that allows a desired color tone to be obtained by adding it to the ink together with other disperse dyes, for example, 0.3 mass relative to the total mass of the ink of the present invention. % Or more and 2.0% by mass or less is preferable.

1-1-4. Blue-based disperse dye The blue-based disperse dye contains D B60 .

Since D B60 has a maximum absorption wavelength of 630 nm or more and 680 nm or less, it has the function of increasing the absorption on the long wavelength side of the ink of the present invention and broadening the wavelength distribution of light that can be absorbed by the ink of the present invention. An image formed with an ink with low absorption on the long wavelength side appears to have a desired color tone under light containing a small amount of long wavelength light, such as light from a fluorescent lamp, but it has long wavelength light such as sunlight. Under light that contains a large amount of light, it may appear reddish due to reflection of long-wavelength light that is difficult to absorb. However, when the ink of the present invention contains D B60 and the absorption on the long wavelength side is increased, the formed image can absorb the long wavelength light more sufficiently. Regardless of the distribution, it looks more similar.

  The content of the blue disperse dye may be an amount that allows the desired color tone to be obtained by being contained in the ink together with other disperse dyes, for example, 0.5 mass with respect to the total mass of the ink of the present invention. % Or more and 3.0% by mass or less is preferable.

1-1-5. Other disperse dyes Other disperse dyes include yellow disperse dyes other than DY1 14, red disperse dyes other than D R92 , D R1 52 or D R1 91, and violet other than D V5 7 or D V9 3 disperse dyes and D B6 0 other blue disperse dye, as well as chromatic dispersion dyes other than the containing green disperse dye. As for the other disperse dyes, only one kind may be contained in the ink of the present invention, or two or more kinds may be contained.

Examples of red disperse dyes other than D R92 , D R1 52, or D R1 91 include D R1 79.

Examples of blue disperse dyes other than D B60 include D B1 83.

  The content of the other disperse dyes is determined by the above method. The coordinate value a * of the ink of the present invention in the CIE L * a * b * color space is −12 to 12 and b * is −32 or more. It may be in a range that is −20 or less.

1-2. Other Components The ink of the present invention may contain a dispersant, a water-soluble organic solvent, a surfactant, or an antiseptic or antifungal agent as long as the effects of the present invention are exhibited. One of these components may be contained in the ink of the present invention, or two or more thereof may be contained.

1-2-1. Dispersant The dispersant can increase the dispersibility of the disperse dye and suppress the generation of bubbles, the gelation of the ink, and the increase in the viscosity of the ink in the ink of the present invention. Dispersants have the ability to affect wetting ability, micronization ability, dispersion stability, dyeability to fabric, fixing rate, leveling property, transferability, fastness and resistance to tarring at high temperatures. In consideration, it can be selected according to the disperse dye.

  Examples of dispersants include formalin condensate of sodium creosote oil sulfonate, formalin condensate of sodium cresol sulfonate and sodium 2-naphthol-6-sulfonate, formalin condensate of sodium cresol sulfonate, sodium phenol sulfonate Formalin condensate, formalin condensate of sodium β-naphthol sulfonate, formalin condensate including sodium β-naphthalene sulfonate and sodium β-naphthol sulfonate, alkylene oxide including ethylene oxide and propylene oxide, fatty alcohol, fatty amine, Alkylatable compounds including fatty acids, phenols, alkylphenols and carboxylic acid amines, lignin sulfonates, sodium paraffin sulfonates, alpha-olefins and Copolymer of water maleic acid, as well as known comb block polymers.

  Examples of comb block polymers include DISPERBYK-190, DISPERBYK-194N, DISPERBYK-2010, DISPERBYK-2015, and BYK-154, BYK Chemie ("DISPERBYK" and "BYK" are registered trademarks of the same company).

  The amount of the dispersant can be 20 parts by mass or more and 200 parts by mass or less when the total mass of the disperse dye is 100 parts by mass. By making the amount of the dispersant 20 parts by mass or more, the dispersibility of the disperse dye is further increased. By setting the amount of the dispersant to 200 parts by mass or less, it is possible to suppress a decrease in injection property due to the dispersant.

  From the viewpoint of increasing the density of the image sample and preventing ejection failure, the dispersant is preferably an acrylic resin having an acid value of 150 mgKOH / g or less.

  Examples of commercially available dispersants that are acrylic resins having an acid value of 150 mgKOH / g or less include DISPERBYK-190, DISPERBYK-2010, DISPERBYK-2015, JONCRYL 586, JONCRYL PDX-6102B, JONCRYL PDX-6124, and JONCRYL JDX. 6500, BASF ("JONCRYL" is a registered trademark of the company), and Floren TG-750W, Kyoeisha Chemical Co., Ltd. are included.

  Examples of other dispersants that can be used in the present invention include JONCRYL 52J and JONCRYL 57J, BASF.

1-2-2. Water-soluble organic solvents Examples of water-soluble organic solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, alcohols containing sec-butanol and t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene Glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, compounds represented by formula (1), other glycerin, hexanetriol, thiodiglycol, 1,2-butanediol, 1,2-pentane Diols, polyhydric alcohols including 1,2-hexanediol and 1,2-heptanediol, ethanolamine, diethanolamine, triethanolamine, N -Methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, amines containing pentamethyldiethylenetriamine and tetramethylpropylenediamine, formamide, N, N An amide containing dimethylformamide and N, N-dimethylacetamide, a heterocyclic compound containing 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone and 1,3-dimethyl-2-imidazolidinone; Sulfoxides, including dimethyl sulfoxide, and alkyl ethers of diethylene glycol, triethylene glycol alkyl ethers and dipropyl It includes glycol ethers containing an alkyl ether of glycol.

In the formula (1), R ₁₁ represents an ethylene glycol group or a propylene glycol group, x, y, and z are all positive integers, and x + y + z = 3-30.

  From the viewpoint of adjusting the penetration of the disperse dye into the fiber structure of the fabric and reducing the color difference between the front and back of the fabric, the water-soluble organic solvent is a polyethylene glycol having a molecular weight of 400 or more and 1000 or less, and a molecular weight of 400 or more and 1000 or less. It is preferable to include at least one selected from polypropylene glycol and a compound represented by formula (1), and from the above viewpoint, polyethylene glycol having a molecular weight of 400 or more and 1000 or less is more preferable.

  The content of these water-soluble organic solvents can be 2% by mass or more and 20% by mass or less based on the total mass of the ink. By setting the content of these water-soluble organic solvents to 2% by mass or more based on the mass of the whole ink, the color tone difference between the front and back sides of the fabric can be further reduced. By setting the content of these water-soluble organic solvents to 20% by mass or less with respect to the mass of the entire ink, it is possible to make it more difficult for the ink to have a high viscosity and to make the inkjet ejection unstable.

  The total amount of the water-soluble organic solvent can be 20% by mass or more and less than 70% by mass with respect to the total mass of the ink of the present invention. By setting the amount of the water-soluble organic solvent to 20% by mass or more with respect to the total mass of the ink of the present invention, the dispersibility of the disperse dye is further increased and the injection property is further increased. By making the amount of the water-soluble organic solvent less than 70% by mass with respect to the total mass of the ink of the present invention, the drying property of the ink of the present invention is improved even when the water-soluble organic solvent is contained.

1-2-3. Surfactants Examples of surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols And nonionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and silicone-based and fluorine-based surfactants.

1-2-4. Examples of antiseptics or antifungal agents include aromatic halogen compounds, methylene dithiocyanates, halogenated nitrogen sulfur compounds, 1,2-benzisothiazolin-3-ones (for example, Proxel GXL (arch chemical) And Proxel are registered trademarks of the company)).

1-3. Physical properties of the ink of the present invention From the viewpoint of further improving the ejection properties of the ink, the viscosity of the ink of the present invention at 25 ° C. is preferably 1 mPa · s or more and 40 mPa · s or less, preferably 5 mPa · s or more and 40 mPa · s or less. More preferably, it is 5 mPa · s or more and 20 mPa · s or less. The viscosity of the ink can be measured at 25 ° C. and 20 rpm with an E-type viscometer (for example, V-25, manufactured by Toki Sangyo Co., Ltd.).

  The surface tension at 25 ° C. of the ink of the present invention is preferably 25 mN / m or more and 50 mN / m or less. If the surface tension is 25 mN / m or more, image bleeding is less likely to occur. When the surface tension is 50 mN / m or less, the ink of the present invention more easily penetrates into the fabric. The viscosity of the ink can be measured by, for example, CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.

1-4. Preparation of Ink The ink of the present invention can be prepared by mixing the disperse dye and water as the color material and the other components optionally contained therein and dispersing the disperse dye. The disperse dye may be dispersed by a disperser including a ball mill, a sand mill, a line mill, and a high-pressure homogenizer. From the viewpoint of preventing nozzle clogging and emitting stably, the disperse dye is preferably dispersed so that the volume average particle size is 300 nm or less and the maximum particle size is 900 nm or less. The volume average particle size of the disperse dye was determined by using a Zetasizer 1000, manufactured by Malvern Co. (“Zeta Sizer” is a registered trademark of Malvern Co., Ltd.), diluted 200 times, and the ink was cooled to room temperature (25 ° C.) by a dynamic light scattering method. Can be measured.

2. Inkjet Textile Printing Method The inkjet textile printing method of the present invention is an inkjet textile printing method characterized in that an image is formed on a fabric with the ink described above. The ink jet textile printing method of the present invention can be carried out in the same manner as a known ink jet textile printing method except that the ink of the present invention described above is an ink jet textile printing ink.

  For example, the ink jet textile printing method of the present invention includes a step of ejecting ink droplets of the present invention from a recording head toward a fabric (image forming step), and applying high-temperature steam to the fabric landed with the ink. A step of fixing the color material contained in the ink of the invention to the fiber of the fabric (coloring step), and a step of washing the fabric having the color material fixed on the fiber to remove the color material that could not be fixed to the fiber (washing step) ). The inkjet textile printing method of the present invention may further include a step of applying a pretreatment agent to the fabric (pretreatment step) or a step of drying the washed fabric (drying step) as necessary.

2-1. Image Forming Process The image forming process is a process for forming a pre-colored image by discharging the ink-jet ink droplets of the present invention from the recording head toward the fabric. For example, an image before color development can be formed by ejecting ink droplets from a recording head and landing on the fabric while moving the fabric relative to a head carriage on which a plurality of recording heads are mounted. . When an image is formed using a plurality of color inks including the ink of the present invention, the ink droplets for each color may be ejected separately or simultaneously. From the viewpoint of suppressing bleeding of the pre-colored image, this step may be performed by heating the fabric as necessary.

2-2. Color development step The color development step is a step in which high temperature steam is applied to the fabric on which an image before color development is formed to fix the color material to the fibers of the fabric. The original hue is developed by the coloring process. Examples of methods for fixing a color material to fabric fibers include steaming, HT steaming, HP steaming, thermofix, alkali pad steam, alkali blotch steam, alkali shock, and alkali cold. Includes fix method. When high temperature steam is applied with an HT steamer, it is preferably treated at 160 ° C. to 180 ° C. for 5 minutes to 20 minutes, and when high pressure steam is applied with an HP steamer, it is about 130 ° C. to 140 ° C. It is preferable to process for 30 minutes.

2-3. Washing step The washing step is a step of washing the fabric after the color development step to remove the color material and the pretreatment agent that could not be fixed to the fibers of the fabric. In this step, it is only necessary to remove the coloring material and the pretreatment agent, and the fabric may be washed with water, or the fabric may be washed with a soaping solution. Examples of the soaping liquid include a mixed liquid of caustic soda, a surfactant, and hydrosulfite.

2-4. Pre-treatment step The method of the present invention provides a pre-treatment step before the image forming step to prevent the ink from bleeding on the fabric and obtain a water-soluble polymer as a paste. You may give the pre-processing agent to contain to a fabric previously. Examples of the method for applying the pretreatment agent include a pad method, a coating method, and a spray method. The applied amount (squeezing rate) of the pretreatment agent may be, for example, 0.2% by mass or more and 90% by mass or less with respect to the total mass of the fabric, although it depends on the type of fabric and its application.

  Examples of the water-soluble polymer include natural water-soluble polymers and synthetic water-soluble polymers. Examples of natural water soluble polymers include starches including corn and wheat, cellulose derivatives including carboxymethylcellulose, methylcellulose and hydroxyethylcellulose, polysaccharides including sodium alginate, guar gum, tamarind gum, locust bean gum and gum arabic, And protein substances including gelatin, casein and keratin. Examples of the synthetic water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, and an acrylic acid polymer.

  The pretreatment agent preferably further contains a pH adjusting agent. From the viewpoint of forming a clear image at a higher density, the pH adjuster is more preferably an acid. Examples of pH adjusters that are acids include citric acid, malic acid and tartaric acid.

  The pretreatment agent may further contain optional components including a reduction inhibitor, a chelating agent, and a preservative as necessary. Examples of the reduction inhibitor include sodium m-nitrobenzenesulfonate. Examples of chelating agents include aminopolycarboxylates, hydroxycarboxylates, polycarboxylates, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid and diethylenetriaminepentaacetic acid. Examples of preservatives include aromatic halogen compounds including isopropyl N- (3-chlorophenyl) carbamate, methylene dithiocyanate and 1,2-benzisothiazolin-3-one.

2-5. Drying step The drying step is a step of drying the washed fabric. Examples of drying methods include non-mechanical drying by squeezing or drying the washed fabric, and mechanical drying by a dryer (heat roll or iron).

2-6. Fabric The fabric is composed mainly of fibers including cellulosic fibers, amide fibers, polyester fibers, polyurethane fibers, and acrylic fibers at least at a site where an image is formed. Examples of fibers include cotton, hemp, wool, silk, viscose rayon, cupra rayon, polynosic, vinylon, nylon, acrylic, polyurethane, rayon polyurethane, polyester and acetate. From the viewpoint that the disperse dye develops well, it is preferable that the fabric includes a portion composed of a polyester fiber, and an image is formed on the polyester fiber portion. From the viewpoint of further improving the fixability of the disperse dye, the radius of the fiber is preferably 10d to 100d.

2-7. Inkjet printing apparatus The image forming step can be carried out by mounting the ink of the present invention on a conventionally known inkjet printing apparatus.

  FIG. 1 is a partial schematic diagram illustrating an example of the configuration of an inkjet recording apparatus. The ink jet recording apparatus includes a transport mechanism 2 that transports a fabric, a head carriage 5 that mounts a plurality of recording heads (not shown) that eject ink jet ink onto the fabric, a warm air mechanism 6 that blows warm air on the fabric, It has an ink tank 7 that can store the ink of the invention, and a vapor mechanism 8 that applies vapor.

  The transport mechanism 2 includes an adhesive belt 21, a support roller 22, a transport roller 23, and a nip roller 24. The adhesive belt 21 is held by the support roller 22 and the conveyance roller 23 and circulates between the support roller 22 and the conveyance roller 23. The nip roller 24 is disposed to face the conveying roller 23 with the adhesive belt 21 interposed therebetween.

  The head carriage 5 and the ink tank 7 communicate with each other, and the ink of the present invention stored in the ink tank 7 is fed from the ink tank 7 to the head carriage 5 when printing.

 The head carriage 5, the steam mechanism 8, and the hot air mechanism 6 are disposed above the fabric P. The recording head mounted on the head carriage 5 is not particularly limited, and may be either a thermal type or a piezo type. The nozzle diameter of the recording head is preferably 10 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less. This is because if the nozzle diameter is less than 10 μm, nozzle clogging due to insoluble matter is likely to occur. On the other hand, when it exceeds 100 μm, the sharpness of the formed image is lowered. Further, the ink droplet size to be ejected is preferably 4 pl or more and 150 pl or less, and more preferably 5 pl or more and 80 pl or less. This is because when the ink droplet size is less than 4 pl, the ejected ink droplets are easily affected by the airflow in the vicinity of the head. On the other hand, when it exceeds 150 pl, the granularity of the formed image is conspicuous. The steam mechanism 8 is a steamer that can apply steam in accordance with an image to be formed. The warm air mechanism 6 includes a fan 6A and a heating element 6B inside, and can control the temperature.

  The ink jet recording apparatus applicable to the present invention may include an ink control unit (not shown) that controls ejection of each color ink in accordance with set image forming conditions.

  When the transport roller 23 is driven, the fabric P disposed on the upper surface of the adhesive belt 21 is transported to the lower surface of the nip roller 24. The fabric P is pressed by the adhesive belt 21 and the nip roller 24 and fixed to the adhesive belt 21. The fabric P fixed to the adhesive belt 21 is conveyed below the head carriage 5. A plurality of recording heads mounted on the head carriage 5 ejects ink droplets of the ink of the present invention fed from the ink tank 7 to a predetermined region (landing possible region) of the fabric to which the pretreatment agent is applied. Landing to form an image. Next, the temperature controllable wind or warm air is blown from the warm air mechanism 6 to dry the image formed on the fabric P.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not construed as being limited by these descriptions. In the following examples, the abbreviations of the components used for preparing the ink are shown in parentheses.

1. Example 1
[Preparation of dispersion]
Disperser DISPERBYK-190 (190), manufactured by BYK Chemie (comb block polymer dispersant, acid value 10 mgKOH / g, solid content 40%) and ion-exchanged water were stirred and mixed until uniform, then Table 1 After adding and premixing each colorant described in the above, Zeta Sizer 1000, made by Malvern (“Zeta Sizer” is a registered trademark of the company), is a sand grinder filled with 50% by volume of 0.5 mm zirconia beads. Dispersions 1 to 9 having a colorant solid content of 20% by mass were prepared by dispersing until the Z-average particle diameter measured by the dynamic light scattering method was in the range of 90 nm to 180 nm. At this time, the dispersing agent and the ion are adjusted so that the content of the coloring material is 20% by mass with respect to the total mass of the dispersing agent and the solid content of the dispersing agent is 30% with respect to the total mass of the coloring material. The amount of exchange water and coloring material was adjusted.

[Preparation of Ink 1]
Dispersion 1, Dispersion 2, Dispersion 7, and Dispersion 8, Ethylene glycol (EG), propylene glycol (PG) and glycerin (GLY) as solvent, KF-351A (351A) as silicone surfactant, Shin-Etsu Chemical Proxel GXL (GXL) manufactured by Kogyo Co., Ltd., Arch Chemical Co., Ltd., and ion-exchanged water are mixed at the following mass ratio, stirred and mixed uniformly, and then filtered through a 1 μm mesh filter. Ink 1 was obtained.
Dispersion liquid 1: 3.0% by mass
Dispersion liquid 2: 5.2% by mass
Dispersion 7: 2.7% by mass
Dispersion 8: 10.0% by mass
EG: 30.0 mass%
PG: 10.0% by mass
GLY: 12.0% by mass
351A: 0.2% by mass
GXL: 0.2% by mass
Ion exchange water: the rest

[Preparation of inks 2 to 9]
Similarly, inks 2 to 9 containing disperse dyes at the mass ratios shown in Table 2 were obtained.

  Table 2 shows the compositions of inks 1 to 9 (each number is% by mass). In Table 2, the “component” column shows the dispersion mixed in each ink, the type of the disperse dye contained in each dispersion, and the abbreviations of the above components.

[Measurement of coordinate values in color space]
Inks 1-9 were diluted 35-fold with water and then diluted 20-fold with acetone. The coordinate values of the diluted inks 1 to 9 in the CIE L * a * b * color space were measured with an ultraviolet-visible spectrophotometer V-650 and JASCO Corporation. For the calculation of coordinate values, a color matching function (JIS Z8701-1999) was used. The values of L *, a * and b * measured for each ink are shown in Table 3.

[Inkjet printing]
Inkjet printer Nassenger-V (manufactured by Konica Minolta Co., Ltd., “Nassenger” is a registered trademark of Konica Minolta IJ Co., Ltd.) using the prepared inks 1 to 9 at a printing rate of 100% duty at 540 dpi × 720 dpi. A 15 cm × 15 cm rectangle was printed on the pretreated polyester fiber.

  As the pretreated polyester fiber, a polyester fiber having a thread thickness of 50d was immersed in an aqueous carboxymethylcellulose solution, and then drawn and dried. After printing, the fabric was subjected to HT steam treatment at 170 ° C. for 10 minutes, then washed with water, reduced and washed with a 0.2% aqueous hydrosulfite solution at 80 ° C., and then sufficiently washed with water and dried.

[Evaluation of image sample]
The image samples thus obtained were subjected to the following evaluations 1 to 3.

[Evaluation 1: Front and back color difference]
The color tone of the front and back of the image sample was visually evaluated according to the following criteria.
A: There is no difference between the color tone of the front surface and the color tone of the back surface.
○: Although there is a slight difference between the color tone of the front surface and the color tone of the back surface, there is little concern.
Δ: Although there is a difference between the color tone of the front surface and the color tone of the back surface, it is acceptable.
X: The difference between the color tone of the front surface and the color tone of the back surface is large and unacceptable.

[Evaluation 2: Edge bleeding]
The image edge of the image sample was visually evaluated according to the following criteria.
A: There is no bleeding at the edge.
○: Slight bleeding on the edge, but little concern.
(Triangle | delta): Although there exists a blur in an edge, it is permissible.
X: Edge blurring is large and unacceptable.

[Evaluation 3: Neutral]
The color tone of the image sample was visually evaluated according to the following criteria.
A: The hue is not felt in the color, and it looks achromatic.
○: A slight color tone is felt, but it is hardly a concern.
Δ: A slight color tone is felt.
X: Reddish, bluish, or other colors added to the achromatic color.

  Table 3 shows the results of evaluations 1 to 3 performed on the image samples obtained with the inks 1 to 9, respectively.

  The ink having the combination of the color materials of the present invention had little color tone difference between the front and back sides and bleeding at the edge, and also had high neutrality (ink Nos. 1 to 7).

When the ink contained D V5 7 as a violet disperse dye, the color difference between the front and back sides was reduced (by comparison between ink Nos. 3-7 and 1-2).

When the ink contains D R9 2 as red disperse dye, edge blurring becomes less (by comparison with the ink No.5~7 and 1-4).

  The ink prepared so that the L value of the coordinate value in the CIE L * a * b * color space obtained from the UV-visible absorption spectrum when the ink is diluted 700 times is more gray even visually. It was possible to form an image that feels like (by comparison between ink Nos. 6 to 7 and 1 to 5).

  On the other hand, the ink having a combination of dyes other than the combination of the present invention had many color difference between the front and back and bleeding at the edge and low neutrality (ink Nos. 8 to 9).

2. Example 2
[Preparation of dispersion]
Dispersant DISPERBYK-190 (190) was replaced with JONCRYL 61J, manufactured by BASF, acid value 195 mg KOH / g (61 J), in the same manner as dispersion 1, dispersion 2, dispersion 6, and dispersion 8. Dispersion 1-1, Dispersion 2-1, Dispersion 6-1, and Dispersion 8-1 were prepared.

  Dispersions having the same composition as Dispersion 1, Dispersion 2, Dispersion 6, and Dispersion 8 were respectively prepared, Dispersion 1-2, Dispersion 2-2, Dispersion 6-2, and Dispersion 8- 2.

  To 78.5 parts by mass of ion-exchanged water, 20 parts by mass of JONCRYL 586 as a dispersant, manufactured by BASF, acid value 108 mgKOH / g (586) and 1.5 parts by mass of sodium hydroxide were added and heated to 60 ° C. While stirring, a 20% by mass aqueous dispersion of a sodium neutralized product of JONCRYL586 was obtained. Dispersant 1-3, Dispersion 2-3, Dispersion 1-3, Dispersion 1-3, Dispersion 1-3, Dispersion 1-3, Dispersion 1-3, Dispersion 1-3, Dispersion 1-3, Dispersion 2-3 Dispersion 6-3 and Dispersion 8-3 were prepared.

[Preparation of Ink 10]
Dispersion 1-1, dispersion 2-1, dispersion 6-1 and dispersion 8-1, ethylene glycol (EG), propylene glycol (PG) and glycerin (GLY) as solvent, KF as silicone surfactant -351A (manufactured by Shin-Etsu Chemical Co., Ltd.), Proxel GXL (manufactured by Arch Chemical Co., Ltd.) as an antifungal agent, and ion-exchanged water are mixed at the following mass ratio, stirred and mixed uniformly, and then a 1 μm mesh filter And ink 10 was obtained.
Dispersion 1-1: 1.5% by mass
Dispersion 2-1: 2.5% by mass
Dispersion 6-1: 5.0% by mass
Dispersion 8-1: 5.0% by mass
EG: 30.0 mass%
PG: 10.0% by mass
GLY: 12.0% by mass
Surfactant: 0.2% by mass
Antifungal agent: 0.2% by mass
Ion exchange water: the rest

[Preparation of Ink 11]
Further, an ink 11 was prepared in the same manner as the ink 10 except that 4.0% by mass of polyethylene glycol 600 (PEG # 600) was contained.

[Preparation of Ink 12]
Further, an ink 12 was prepared in the same manner as the ink 10 except that 4.0% by mass of polypropylene glycol 400 (PPG400) was contained.

[Preparation of ink 13]
Further, an ink 13 was prepared in the same manner as the ink 10 except that 4.0% by mass of Liponic EG-1 (formula (1)) Lipo Chemicals was included. This compound is a compound in which x + y + z = 26 in the formula (1).

[Preparation of Ink 14]
Dispersion 1-1, dispersion 2-1, dispersion 6-1 and dispersion 8-1 were defined as dispersion 1-2, dispersion 2-2, dispersion 6-2 and dispersion 8-2, respectively. Except that, ink 14 was prepared in the same manner as ink 10.

[Preparation of Ink 15]
Dispersion 1-1, dispersion 2-1, dispersion 6-1 and dispersion 8-1 were designated as dispersion 1-3, dispersion 2-3, dispersion 6-3 and dispersion 8-3, respectively. Except for the above, ink 15 was prepared in the same manner as ink 10.

  Table 4 shows the compositions of inks 10 to 15 (each number is% by mass). In Table 4, the “component” column shows the dispersion mixed in each ink, the type of the dispersant contained in each dispersion, and the abbreviations of the respective components. In Table 4, the “acid value” column shows the acid value (unit: mgKOH / g) of the dispersant contained in the dispersion.

[Measurement of coordinate values in color space]
Inks 10 to 15 were diluted 35 times with water and then further diluted 20 times with acetone. The coordinate values of the diluted inks 1 to 9 in the CIE L * a * b * color space were measured with an ultraviolet-visible spectrophotometer V-650 and JASCO Corporation. The L *, a * and b * values measured for each ink are shown in Table 5.

[Evaluation 4: Concentration]
Inkjet printer Nassenger-V (made by Konica Minolta Co., Ltd., “Nassenger” is a registered trademark of Konica Minolta IJ Co., Ltd.) using the prepared inks 10 to 15 at a printing rate of 100% Duty at 540 dpi × 720 dpi. A 15 cm × 15 cm rectangle was printed on the pretreated polyester fiber.

The density of the image sample was evaluated with a spectrocolorimeter (SP60 series) Model SP62, manufactured by X-RITE Co., Ltd., and visually according to the following criteria.
(Double-circle): The numerical value of a colorimeter is 50 or less, and it is evaluated that sufficient density has come out to the image sample visually.
◯: Although the numerical value of the colorimeter is greater than 50, it is judged by visual observation that a sufficient density appears in the image sample.
X: The value of the colorimeter is larger than 50, and it is determined that a sufficient density is not obtained in the image sample by visual observation.

[Evaluation 5: Injection property]
In a low humidity environment of 25 ° C. and a relative humidity of 30%, each ink was ejected from the inkjet printer Nassenger-V at a printing rate of 100% Duty. At the time of re-ejection, out of 256 nozzles, the number of non-ejecting nozzles, the number of nozzles with different ejection angles (curved nozzles), and whether or not micro splashes (splashes) other than main droplets occur When these occurred, it was determined that dry fixation occurred at the nozzle during the stop.
A: No non-ejection nozzles are generated after re-ejection, and there is no increase in splashing.
○: After re-ejection, about 1 to 2 bent nozzles are generated, but there is no influence on the image quality and there is no increase in splashing.
X: Three or more non-ejection nozzles were generated after re-ejection, splashing was conspicuous, and image quality deteriorated to an unacceptable level.

Table 5 shows the results of evaluation 4 performed on the image samples obtained with each of the inks 10 to 15 and the results of evaluation 5 performed on the ejection properties of the inks 10 to 15.

  The ink having the combination of color materials of the present invention further contains at least one selected from polyethylene glycol having a molecular weight of 400 to 1000, polypropylene glycol having a molecular weight of 400 to 1000, and a compound represented by the formula (1). As a result, the density of the image sample became higher (by comparison between ink Nos. 11 to 13 and 10).

  When the ink having the combination of the color materials of the present invention further contains an acrylic resin having an acid value of 150 or less, the density of the image sample becomes higher and ejection defects are less likely to occur (Ink Nos. 14 to 15). (Compared with 10).

  The ink of the present invention can be suitably used for dyeing fabrics, particularly gray dyeing, by discharging from an ink jet textile printing apparatus.

P fabric 2 transport mechanism 5 head carriage 6 warm air mechanism 6A fan 6B heating element 7 ink tank 8 vapor mechanism 21 adhesive belt 22 support roller 23 transport roller 24 nip roller

Claims (8)

A water-based ink for ink jet printing containing water and a coloring material,
The coloring material includes a yellow disperse dye, a red disperse dye, a violet disperse dye, and a blue disperse dye,
The yellow disperse dye is C.I. I. Disperse Yellow 114,
The red disperse dye is C.I. I. Disperse Red 92, C.I. I. Disperse Red 152 and C.I. I. Disperse Red Including at least one selected from the group consisting of 191;
The violet disperse dye is C.I. I. Disperse Violet 57 and C.I. I. Disperse Violet Including one or both of 93,
The blue disperse dye is C.I. I. Disperse Blue 60,
The a * in the CIE L * a * b * color space obtained from the UV-visible absorption spectrum of the ink diluted 35-fold with water and 35-fold with acetone and then diluted 20-fold with acetone is 12 or more and 12 An aqueous ink, wherein b * is −32 or more and −20 or less. The violet disperse dye is C.I. I. Disperse Violet The water-based ink according to claim 1, comprising 57. The red disperse dye is C.I. I. Disperse Red The water-based ink according to claim 1, wherein the water-based ink comprises 92.   4. The L * in the CIE L * a * b * color space obtained from an ultraviolet-visible absorption spectrum when the ink is diluted 700 times is 50 or more. 5. The water-based ink described in 1. It further contains at least one selected from the group consisting of a polyethylene glycol having a molecular weight of 400 or more and 1000 or less, a polypropylene glycol having a molecular weight of 400 or more and 1000 or less, and a compound represented by the formula (1). The aqueous ink according to any one of 1 to 4.

(In formula (1), R ₁₁ independently represents an ethylene glycol group or a propylene glycol group, and x, y, and z are all positive integers, and x + y + z = 3 to 30.)   The water-based ink according to any one of claims 1 to 5, further comprising an acrylic resin having an acid value of 150 mgKOH / g or less.   An ink-jet printing method comprising forming an image on a fabric with the water-based ink according to claim 1.   The ink-jet printing method according to claim 7, wherein the fabric includes a portion made of a polyester fiber, and the image is formed on the portion.

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