JP2010069817A - Ink-jet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink-jet recording method using an ink-jet printing system which eliminates pretreatment for a cloth, suppresses bleeding on an image, and obtains a high-density printed matter. <P>SOLUTION: In the ink-jet recording method, printing is performed on a cloth not having an ink receiving layer by discharging an aqueous dye ink containing an acid dye or a direct dye as a water-soluble dye, and a water-soluble resin which has a carboxyl group or a sulfo group as an acid group, and has an acid value of ≥70 mgKOH/g and ≤300 mgKOH/g, ≥1.0 g/m<SP>2</SP>of urea is added to the cloth, and the cloth is subjected to heat treatment at a temperature of ≥150°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ink jet recording method for forming an image on a fabric by an ink jet printing method using an aqueous dye ink.

  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 high gradation. Furthermore, since only a necessary amount of ink as a formed image is used for image formation, 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.

  However, in the case of ink-jet printing, unlike the normal printing method, the viscosity of the ink used is low, so when printing on the fiber as it is, the ink bleeds along the fibers constituting the fabric and the image quality is greatly reduced. And a problem of insufficient fixing of the image. For this reason, when an image such as a pattern is formed on a fabric by the ink jet method, the fabric is pretreated with a water repellent, a printing paste or the like before printing in order to increase the obtained color density or to suppress bleeding. Generally, a method of forming an ink receiving layer on a fabric is performed. In addition, after printing on the fabric, it is necessary to provide a fixing step of performing a heat treatment by steaming in order to fix a color material such as a dye on the fabric, which is compared with the convenience of image formation by the ink jet recording method. However, the ink-jet textile printing method is complicated and time-consuming, and the current situation is that the advantages of the ink-jet method are not fully utilized. Therefore, it is desired to develop a system that can obtain a high-quality print even on a fabric that has not been pretreated, and that does not require complicated post-treatment.

In addition, a technique is disclosed in which a polymer compound that crosslinks with a dye and an active energy ray is contained to eliminate the need for pretreatment (for example, see Patent Document 1). However, electron beams and ultraviolet rays are used as active energy ray sources, and these active energy ray irradiation devices are expensive and large-scale.
JP 2007-186539 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an ink jet recording method using an ink jet printing method that eliminates the need for pre-processing on a fabric, suppresses image bleeding, and provides a high-density printed matter. Is to provide.

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

1. A water-soluble resin having an acid dye or a direct dye as a water-soluble dye, a carboxyl group or a sulfo group as an acid group, and an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less on a fabric having no ink receiving layer Ink jet, characterized in that after the water-based dye ink containing the ink is discharged and printed, urea is applied to the fabric in an amount of 1.0 g / m ² or more, and then the fabric is subjected to a heat treatment at a temperature of 150 ° C. or more. Recording method.

  2. 2. The ink jet recording method according to 1 above, wherein the fabric is heated to a temperature of 40 ° C. or higher when the water-based dye ink is discharged onto the fabric.

  According to the present invention, it is possible to provide an ink jet recording method using an ink jet textile printing method in which pre-treatment on a fabric is unnecessary, image bleeding is suppressed, and a high density printed matter can be obtained.

  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 an acid dye or direct dye as a water-soluble dye and a carboxyl group or a sulfo group as an acid group, and has an acid value of 70 mgKOH / g or more and 300 mgKOH / g. After discharging and printing water-based dye ink containing the following water-soluble resin, urea is applied to the fabric in an amount of 1.0 g / m ² or more, and then the fabric is subjected to heat treatment at a temperature of 150 ° C. or more. The present invention has found that an ink jet recording method can be realized that eliminates the need for pre-treatment on the fabric, suppresses image blurring, and provides a high-density printed matter. It depends on you.

  The ink jet recording method having the above-described configuration defined in the present invention can eliminate the need for the pre-treatment of the fabric, suppress the image bleeding, and obtain a high-density printed matter as follows. ing.

  That is, by adding urea having deliquescent properties to the ink, water necessary for the color development reaction is secured, and high density color development is achieved by high-temperature color development at a temperature of 150 ° C. or higher. As specified in Item 2, preferably, when printing is performed, the fabric is heated to 40 ° C. or more to evaporate the water in the ink that has landed on the fabric, thereby quickly concentrating the ink, thereby increasing the viscosity. It was possible to prevent image bleeding.

  Hereinafter, details of each component of the ink jet recording method of the present invention will be described.

<Water-based dye ink>
The aqueous dye ink according to the present invention (hereinafter also simply referred to as ink) has at least an acid dye or a direct dye as a water-soluble dye and a carboxyl group or a sulfo group as an acid group, and has an acid value of 70 mgKOH / g or more and 300 mgKOH. / G or less of water-soluble resin.

(Water-soluble dye)
As the color material used in the aqueous dye ink according to the present invention, an acid dye or a direct dye is used. Preferably, an acid dye is preferable in consideration of dyeability and fastness to a fabric.

  Hereinafter, specific examples of dyes applicable to the aqueous dye ink according to the present invention (hereinafter also simply referred to as ink) will be listed, but the present invention is not limited to these exemplified dyes.

  Examples of water-soluble dyes that can be used in the present invention include azo dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes, and diphenylmethane dyes.

(Acid dyes)
<C. I. Acid Yellow>
1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 42, 44, 49, 59, 61, 65, 67, 72, 73, 79, 99, 104, 110, 114, 116, 118, 121, 127, 129, 135, 137, 141, 143, 151, 155, 158, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 220, 230, 232, 235, 241, 242, 246,
<C. I. Acid Orange>
3, 7, 8, 10, 19, 22, 24, 51, 56, 67, 74, 80, 86, 87, 88,
89, 94, 95, 107, 108, 116, 122, 127, 140, 142, 144, 149, 152, 156, 162, 166, 168,
<C. I. Acid Red>
88, 97, 106, 111, 114, 118, 119, 127, 131, 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415, 447,
<C. I. Acid Violet>
17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126,
<C. I. Acid Blue>
1, 7, 9, 15, 23, 25, 40, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350,
<C. I. Acid Green>
9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109,
<C. I. Acid Brown>
2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413,
<C. I. Acid Black>
1, 2, 3, 24, 26, 31, 50, 52, 52: 1, 58, 60, 63, 107, 109, 112, 119, 132, 140, 155, 172, 187, 188, 194, 207, 222,
(Direct dye)
<C. I. Direct yellow>
8, 9, 10, 11, 12, 22, 27, 28, 39, 44, 50, 58, 79, 86, 87, 98, 105, 106, 130, 132, 137, 142, 147, 153,
<C. I. Direct orange>
6, 26, 27, 34, 39, 40, 46, 102, 105, 107, 118,
<C. I. Direct Red>
2, 4, 9, 23, 24, 31, 54, 62, 69, 79, 80, 81, 83, 84, 89, 95, 212, 224, 225, 226, 227, 239, 242, 243, 254,
<C. I. Direct Violet>
9, 35, 51, 66, 94, 95,
<C. I. Direct Blue>
1, 15, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 160, 168, 189, 192, 193, 199, 200, 201, 202, 203, 218, 225, 229, 237, 244, 248, 251, 270, 273, 274, 290, 291,
<C. I. Direct Green>
26, 28, 59, 80, 85,
<C. I. Direct Brown>
44, 106, 115, 195, 209, 210, 222, 223,
<C. I. Direct Black>
17, 19, 22, 32, 51, 62, 108, 112, 113, 117, 118, 132, 146, 154, 159, 169
The concentration of these dyes in the ink is preferably 0.1 to 20% by mass, and more preferably 0.2 to 13% by mass. If it is 0.1% by mass or less, the coloring density is insufficient, and if it is 20% by mass or more, the precipitation of dye occurs or the viscosity becomes too high, resulting in unstable ejection.

(Water-soluble resin)
The water-soluble resin applied to the ink according to the present invention has a carboxyl group or a sulfo group as an acidic group, and has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less.

  As such a resin, a resin having a hydrophobic component and a hydrophilic component in a certain balance is designed and used. In this case, the hydrophilic component is ionic, and more preferably anionic. In particular, those that are rendered water-soluble by neutralizing anionic substances with a volatile base component are preferred. The water-soluble resin of the present invention is a resin having a carboxyl group or a sulfonic acid group as an acidic group and having an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less. An acid value of about 90 mgKOH / g to 200 mgKOH / g can be particularly preferably used.

  The acid value is the number of milligrams of potassium hydroxide (mgKOH / g) required to neutralize the acidic component contained in 1 g of resin.

  Examples of such resins include acrylic resins, styrene-acrylic resins, acrylonitrile-acrylic resins, vinyl acetate-acrylic resins, polyurethane resins, and polyester resins.

  As the resin, a resin containing a hydrophobic monomer and a hydrophilic monomer can be used.

  Examples of hydrophobic monomers include acrylic acid esters (such as n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylic acid esters (such as ethyl methacrylate, butyl methacrylate, glycidyl methacrylate), and styrene. Etc.

  Examples of the hydrophilic monomer include acrylic acid, methacrylic acid, acrylamide and the like, and those having an acidic group such as acrylic acid can preferably be those neutralized with a base after polymerization.

  As the molecular weight of the resin, an average molecular weight of 3000 to 30000 can be used. Preferably, 7000 to 20000 can be used.

  Resin having a Tg of about -30 ° C to 100 ° C can be used. Preferably, about -20 ° C to 80 ° C can be used.

  As the polymerization method, it is preferable to use solution polymerization.

  The acidic group derived from the acidic monomer of the resin is preferably partially or completely neutralized with a base component. As the neutralizing base in this case, an alkali metal-containing base such as sodium hydroxide or potassium hydroxide, or an amine (ammonia, alkanolamine, alkylamine, etc. can be used) can be used.

  The addition amount of the water-soluble resin is preferably 2% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 6% by mass or less in order to obtain the object of the present invention. preferable.

  In the present invention, the reason why it is preferable to use a water-soluble resin having a solid content of 2% by mass or more and 10% by mass or less is presumed as follows.

  If it is less than 2% by mass, the degree of thickening is small and the ink mixing is insufficiently prevented, and high image quality cannot be obtained. Moreover, if it is added more than 10% by mass, the storage stability and ejection stability of the ink will be unstable.

[Various additives]
In the ink according to the present invention, various additives can be used as necessary in addition to the above-described acidic dye or direct dye and water-soluble resin.

(Water-soluble organic solvent)
In the ink according to the present invention, various water-soluble organic solvents can be used for the purpose of adjusting ink viscosity.

  Examples of the water-soluble organic solvent applicable to the ink according to the present invention include glycol ethers (for example, ethylene glycol monoethyl, ethylene glycol monobutyl, diethylene glycol monobutyl, triethylene glycol monobutyl, propylene glycol monopropyl, dipropylene). Propylene glycol monomethyl, tripropylene glycol monomethyl, etc.), 1,2-alkanediols (for example, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, etc.) Alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, etc.), polyhydric alcohols (eg, ethylene glycol) , Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), amines (eg, ethanolamine, diethanolamine) , Triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.) Amides (eg, formamide, N, N-dimethylformami , N, N-dimethylacetamide, etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxide (For example, dimethyl sulfoxide, etc.).

  The addition amount of the water-soluble organic solvent is preferably 10% by mass or more and less than 80% by mass. More preferably, it is 15 mass% or more and less than 75 mass%.

(Surfactant)
In the present invention, from the viewpoint of imparting permeability to the fabric and sufficient wettability, the surface tension of the ink is preferably 40 mN / m or less, and more preferably 35 mN / m or less. In order to adjust to this surface tension, various surfactants can be preferably used. In particular, it is effective to use at least one selected from a silicone-based surfactant and a fluorine-based surfactant having a perfluoroalkenyl group.

  Silicone surfactants are those in which the side chain or terminal of dimethylpolysiloxy acid is polyether-modified, such as KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., and BYK347 and BYK348 manufactured by Big Chemie are commercially available. ing.

  A fluorosurfactant having a perfluoroalkenyl group is synthesized by introducing a hydrophilic group into a dimer, trimer or pentamer obtained by anionic polymerization of 4-fluoroethylene or hexafluoropropylene. Any of a nonionic type having a polyoxyethylene ether in a hydrophilic group, an anionic type having a sulfonic acid or a carboxylic acid, and a betaine type having a quaternary ammonium salt and a carboxylic acid can be preferably used. It is marketed as the Footage series.

  In addition to the fluorine-based or silicone-based surfactant, the following surfactants can be used in the ink according to the present invention. For example, anionic surfactants such as alkyl sulfates, alkyl ester sulfates, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, fatty acid salts, polyoxyethylene alkyl Nonionic surfactants such as ethers, polyoxyalkylene alkylphenyl ethers, acetylene glycols, polyoxyethylene-polyoxypropylene block copolymers, activities such as glycerin esters, sorbitan esters, polyoxyethylene fatty acid amides, amine oxides Agents, cationic surfactants such as alkylamine salts and quaternary ammonium salts.

(Other additives)
In the ink according to the present invention, an antiseptic and an antifungal agent may be added to the inkjet ink in order to maintain long-term storage stability. Examples of the antiseptic and 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.

"urea"
In the ink jet recording method of the present invention, after applying the aqueous dye ink according to the present invention to a fabric, 1.0 g / m ^{2 of} urea is used as a dyeing aid for enhancing the dyeing efficiency of the water-soluble dye on the fabric. It is characterized by being given above, preferably 1.0 g / m ² or more and 6.0 g / m ² or less, more preferably 1.0 g / m ² or more and 4.0 g / m ² or less.

<Inkjet recording method>
Next, a method for producing a printed material by the ink jet recording method of the present invention will be described.

As main steps used in the inkjet recording method of the present invention,
1) A printing process in which a water-based dye ink containing a water-soluble dye (acidic dye or direct dye) and a water-soluble resin according to the present invention is applied onto a cloth by an ink jet method. At this time, the cloth is heated to 40 ° C. or higher. Printing is preferable from the viewpoint of preventing bleeding and the like,
2) A dyeing process for applying urea according to the present invention on a printed fabric;
3) a heat treatment step of heating the fabric at 150 ° C. or higher,
And 4) a cleaning process for removing unnecessary substances in the printed fabric.

[Fabric]
The fiber material constituting the fabric mainly used in the inkjet recording method of the present invention is not particularly limited as long as it contains fibers that can be dyed with an acid dye or a direct dye, such as cotton, silk, wool, nylon, Various fiber materials such as polyester, rayon, acrylic fiber and the like may be mentioned, and these may be a blend, a woven fabric, a non-woven fabric, or the like.

[Printing process]
In the inkjet recording method of the present invention, the application of the aqueous dye ink onto the fabric is performed using an inkjet recording head.

  The ink jet recording head used in the ink jet recording method of the present invention may be an on-demand system or a continuous system. Discharge methods include electro-mechanical conversion methods (single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (thermal ink jet type, bubble type) Specific examples include jet (registered trademark) type, electrostatic suction type (electric field control type, slit jet type, etc.) and discharge type (spark jet type, etc.). You may use. As a recording method of the ink jet printer, either a serial head method or a line head method can be used.

  As a condition for ejecting the inkjet ink according to the present invention from the inkjet recording head, it is preferable to perform recording using an inkjet recording head having a nozzle diameter of 10 to 50 μm in order to obtain a high-definition image. 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 40 μm is particularly preferable.

  The drive frequency of the ink jet head drive device is preferably 15 kHz or more, and more preferably 30 kHz or more and 100 kHz or less from the viewpoint of preventing 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 recording method of the present invention, the droplet volume at the time of ink flight is preferably 10 pl or more and 50 pl or less from the viewpoint of improvement in bleeding resistance and sharpness.

  In the ink jet recording method of the present invention, when the aqueous dye ink is applied onto the cloth using the ink jet recording head, the cloth itself is preferably heated to 40 ° C. or higher, more preferably 40 ° C. or higher, 80 Heating to below ℃.

  Printing in a state where the fabric is heated under the above temperature condition is preferable from the viewpoint of promptly increasing the viscosity of the ink droplets that have landed on the fabric and exhibiting the effect of preventing bleeding.

  The method for heating the fabric is not particularly limited, but a method of heating the platen that supports the conveyance of the fabric to a desired temperature with a flat panel heater or the like is simple and preferable.

[Dyeing process to give urea]
In the ink jet recording method of the present invention, there is no particular limitation on the application order of the aqueous solution containing water-soluble dye ink and urea at a predetermined concentration to the fabric, but urea is immediately applied after applying the aqueous dye ink onto the fabric. A method of applying an aqueous solution containing a predetermined concentration and dyeing an acid dye or a direct dye on a fabric is preferred.

  The method for applying the aqueous urea solution to the fabric holding the aqueous dye ink in a wet state is not particularly limited as long as it is an apparatus that can uniformly supply liquid, and the inkjet head system as described above. A coater method, a roller method, a spray method, and the like can be appropriately selected and used.

  As the ink jet head system, the same ink jet head as that used for applying the aqueous dye ink can be applied.

  FIG. 1 is a schematic view showing an example of a method for applying an aqueous dye ink and an aqueous urea solution using a line head type inkjet head.

In a) of FIG. 1, the line head type inkjet heads H _Y , H _M , H _C , H for conveying the fabric P from the upper part to the lower part and discharging the aqueous dye ink covering the entire width of the fabric P. and _K, is the ink-jet head H _U of the line head method of discharging the corresponding urea aqueous solution, respectively are disposed respectively. On the fabric P being conveyed continuously, after discharging the water-based yellow dye ink from the ink jet head H _Y, immediately ejected from the urea solution the inkjet head H _UA, successively, water-based magenta dye ink and the urea aqueous solution, water-based cyan dye ink And a urea aqueous solution, a water-based black dye ink, and a urea aqueous solution are discharged to form a print image.

Further, in the method described in FIG. 1 b, line head type inkjet heads H _Y , H _M , H _C , and H _K are arranged as a group on the upstream side, and one urea aqueous solution is discharged on the downstream side. a configuration of arranging the ink-jet head H _U of the line head type, a in FIG. 1) may be any structure of b) in FIG.

  FIG. 2 is a schematic view showing another example of a method for applying an aqueous dye ink and a urea / alkali aqueous solution using a line head type inkjet head.

In FIG. 2, the line head type inkjet heads H _Y , H _M , H _C , and H _K that discharge the aqueous dye ink and the line head type inkjet head H _U that discharges the urea aqueous solution are joined to each other. This is a line head type inkjet head unit.

  FIG. 3 is a bottom view of an ink jet head unit including the ink jet head for discharging the aqueous dye ink shown in FIG. 2 and a line head type ink jet head for discharging an aqueous urea solution.

Bottom view shown in FIG. 3, as an example an ink jet head unit HU _Y in FIG. 2, there is shown the arrangement of the nozzles N as viewed from the bottom side, in order from the upstream side in the transport direction of the recording medium, based yellow and the ink jet head H _Y nozzle array for ejecting a dye ink is provided, the ink-jet head H _UA which nozzle rows are provided for discharging the aqueous urea solution is disposed. The nozzles of the inkjet heads H _Y and H _U are at the same position in the nozzle row direction. The nozzle pitch of each nozzle row is X / 2 (mm), and is set to be equal to the dot pitch X / 2 in the direction perpendicular to the conveyance direction of the obtained recording medium.

  In addition, although the printing process and the dyeing process using the inkjet head have been described using a line head inkjet head, a serial head system in which each inkjet head independently moves in the width direction of the fabric is used. It may be used. For example, a method in which an inkjet head that independently ejects a serial head aqueous dye ink and an inkjet head that also ejects a serial head urea aqueous solution are arranged in parallel on the downstream side, or is aqueous on a carriage. A serial head type ink jet recording method or the like in which an ink jet head that discharges dye ink is provided and an ink jet head that discharges an aqueous urea solution is disposed at both ends thereof can be used.

  Moreover, in a dyeing process, as a method of providing urea aqueous solution, it can provide using a spray coating device. The spray coating apparatus is a method of supplying a urea aqueous solution as a group of fine droplets from a spray nozzle while pressurizing.

  Further, as a method for applying the urea aqueous solution, a conventionally known wet coating apparatus can be applied. For example, a dip coating apparatus, a roller coating apparatus, a fountain coating apparatus, a gravure coating apparatus, a blade coating apparatus, a bar coating apparatus, a slide A coating device, an extrusion coating device, or the like can be applied.

[Heat treatment process]
The fabric printed in the printing process and the dyeing process is then subjected to heat treatment. By performing this heat treatment, the acid dye or the direct dye is completely fixed to the fibers constituting the fabric.

  The heating temperature in the heat treatment step is characterized by heating at 150 ° C. or higher, but the upper limit is preferably 250 ° C. depending on the characteristics of the fibers constituting the fabric to be used.

  The heating method that can be applied in the heat treatment step is not particularly limited, but the printed fabric can be heated to a desired temperature using a heating fan, a flat panel heater, a radiant heat heating means, a heating roller, or a heating belt. it can.

[Washing process]
After the heat treatment, washing may be performed for the purpose of removing the dye that was not involved in the dyeing. The method is selected according to the material to be printed, the ink type, and the pre-processing contents for the printed matter. There are many cases that end with water washing, but when fastness is required, it is effective to perform water washing, hot water washing and soaping. You may dry after washing | cleaning. After the washed fabric is squeezed or dehydrated, it is dried or dried using a dryer, heat roll, iron or the like.

[Printing process line]
Next, the entire line of the textile printing process will be described using the above-described ink jet recording method of the present invention.

  FIG. 4 is a schematic line diagram showing the flow of each step in the inkjet recording method of the present invention.

  FIG. 4A is a line diagram including a printing process in which an aqueous dye ink and an aqueous urea solution are applied using the line head type inkjet head described in FIG.

  In FIG. 4 a), the aqueous dye ink INK is ejected from the nozzle N using the inkjet head 1 in the printing process A onto the fabric P that is continuously conveyed. At this time, it is preferable that the fabric P is heated to 40 ° C. or higher by the flat panel heater 8 installed on the back surface of the fabric P from the viewpoint of preventing bleeding and obtaining a high-definition image. After the aqueous dye ink INK is discharged onto the fabric P, immediately after the dyeing process B, the urea aqueous solution U is applied using the inkjet head 2 in the same manner.

  Next, the fabric P is moved to the heat treatment step C, and the printing portion is heated and pressed to be fixed by passing the fabric P between the nip formed by the heating roller 9 and the support roller 10 as a heating means. Next, the heat-treated fabric is moved to the cleaning step D, and washed and dried to create a printed matter.

  FIG. 4B shows a method in which the urea aqueous solution U is sprayed and landed on the fabric P using the spray coating device 3 as means for applying the urea aqueous solution U onto the fabric P.

  FIG. 4 c) shows a method of applying the urea aqueous solution U onto the fabric P using the roller coating device 4. The roller which comprises the roller coating device 4 is comprised by the sponge roller provided with the sponge which hold | maintains a solution on the surface of metal core bars. Sponge rollers include, for example, cellulose sponge, polyvinyl alcohol sponge, urethane foam, ethylene-vinyl acetate copolymer (EVA) sponge, melamine foam, resin foam such as polyethylene foam, natural rubber (NR) sponge, chloroprene rubber (CR ) Sponges, ethylene-propylene rubber (EPDM) sponges, rubber-based sponges such as butadiene-acrylonitrile rubber sponges, and the like. Among these, the sponge portion is made of resin-based sponge, and after supplying the urea aqueous solution to the sponge constituting the roller coating device 4 from the urea aqueous solution supply unit 5 located at the top of the roller coating device 4, the sponge portion is re-applied to the fabric. It is a supply method.

  FIG. 4 d) shows a method in which the urea aqueous solution U is applied to the fabric P by using a constant supply type extrusion coating apparatus 6.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

<< Preparation of water-based dye ink set >>
[Preparation of ink set 1]
An ink set 1 comprising aqueous dye inks of the following colors was prepared.

(Preparation of yellow ink 1)
C. I. Acid Yellow 79 5%
Jonkrill 70J (BASF water-soluble resin, 30% aqueous solution, oxidation 240, Tg 102 ° C., average molecular weight 16500) 10%
Diethylene glycol monobutyl ether 25%
Diethylene glycol monoethyl ether 20%
KF-351A (Shin-Etsu Chemical Co., silicone surfactant) 0.5%
The above additives were mixed and stirred, and ion-exchanged water was added to make the total amount 100 parts, followed by filtration with a 5 μm filter to obtain yellow ink 1.

(Preparation of magenta ink 1)
In the preparation of the yellow ink 1, C.I. I. In place of Acid Yellow 79, C.I. I. Magenta ink 1 was obtained in the same manner except that Acid Red 249 was used.

(Preparation of cyan ink 1)
In the preparation of the yellow ink 1, C.I. I. In place of Acid Yellow 79, C.I. I. Cyan ink 1 was obtained in the same manner except that Direct Blue 87 was used.

(Preparation of black ink 1)
In the preparation of the yellow ink 1, C.I. I. In place of Acid Yellow 79, C.I. I. Black ink 1 was obtained in the same manner except that Acid Black 52: 1 was used.

(Preparation of light magenta ink 1)
C. I. Acid Red 249 1%
Jonkrill 70J (BASF water-soluble resin, 30% aqueous solution, oxidation 240, Tg 102 ° C., average molecular weight 16500) 10%
Diethylene glycol monobutyl ether 25%
Diethylene glycol monoethyl ether 45%
KF-351A (Shin-Etsu Chemical Co., silicone surfactant) 0.5%
The above additives were mixed and stirred, and ion-exchanged water was added to make the total amount 100 parts, followed by filtration with a 5 μm filter to obtain light magenta ink 1.

(Preparation of light cyan ink 1)
In the preparation of the light magenta ink 1, the C.I. I. Instead of Acid Red 249, C.I. I. A light cyan ink 1 was obtained in the same manner except that Direct Blue 87 was used.

[Preparation of ink set 2]
In the preparation of the ink set 1, Joncrill 70J (water soluble resin manufactured by BASF, 30% aqueous solution, oxidation 240, Tg 102 ° C., average molecular weight 16500), which is a water-soluble resin used for the preparation of each color ink, was used. Ink sets 2 were prepared in the same manner except that each was changed to (BASF water-soluble resin, 29.5% aqueous solution, oxidation 74, Tg 65 ° C., average molecular weight 10,000).

[Preparation of ink set 3]
In preparation of the ink set 1, except that Jonkrill 70J (BASF water-soluble resin, 30% aqueous solution, oxidation 240, Tg 102 ° C., average molecular weight 16500), which is a water-soluble resin used for the preparation of each color ink, was removed. Similarly, each color ink was prepared, and this was designated as ink set 3.

<< Preparation of aqueous urea solution >>
Urea 10.0g
Diethylene glycol monobutyl ether 8.0g
Diethylene glycol 23.0g
Glycerin 4.5g
Olfine E1010 (Nisshin Chemical Co., Ltd.) 5.3g
Aqueous urea solution was prepared by adding ion exchanged water to a total volume of 100 ml.

<Inkjet image recording>
[Recording method 1]
The ink set 1 prepared above, the configuration according to FIG. 2, FIG. 3, and discharges the ink-jet head H _U, the ink jet head and the urea aqueous solution for light cyan ink further discharging the inkjet head and the urea aqueous solution for light magenta ink jet It was loaded respectively Konica Minolta IJ piezoelectric inkjet head Co., Ltd. with a head H _U. The inkjet recording head for water-based dye ink has a nozzle diameter of 28 μm, a driving frequency of 18 kHz, a nozzle number of 512, a minimum liquid amount of 14 pl, a nozzle density of 180 dpi (dpi represents 1 nozzle, that is, the number of nozzles per 2.54 cm), A single-color solid image (printing density 100%), a 250 μm single-color thin line image, and each color white character image were printed on the cloth for each color. The printing process was performed in an environment of 20 ° C. and a relative humidity of 55%.

Further, the inkjet head H _U is loaded with an aqueous urea solution, after ejecting each color aqueous dye ink onto the cloth was discharged immediately. The discharge condition was applied under the condition that the application amount of urea was 2.0 g / m ² . In addition, the used cloth used the silk cloth which does not have an ink receiving layer.

  Further, when each color aqueous dye ink and urea aqueous solution were applied to the fabric, the fabric was heated by a flat panel heater disposed at the lower part of the fabric so that the printing surface temperature of the fabric would be 50 ° C.

  Next, in the heat treatment step, the fabric was heated at 180 ° C. for 5 minutes in a heating zone equipped with a heating fan, and then washed to obtain a printed matter.

[Recording methods 2, 3]
In the recording method 1, a printed matter was produced in the same manner except that the ink sets 2 and 3 were used in place of the ink set 1, and these were designated as recording methods 2 and 3.

[Recording method 4]
In the above recording method 1, a printed matter was prepared in the same manner except that the urea aqueous solution was not applied in the dyeing step, and this was designated as recording method 4.

[Recording methods 5 to 7]
In the recording method 1, the application amount of urea in the dyeing process, respectively ^{0.5g / m 2, 1.0g / m} 2, except that the 5.0 g / ^{m 2} in the same manner to create the printed matter These were designated as recording methods 5 to 7.

[Recording method 8]
In the above recording method 1, a printed matter was prepared in the same manner except that the fabric was not heated in the printing process, and this was designated as recording method 8.

[Recording method 9]
In the above recording method 1, a printed matter was prepared in the same manner except that the heat treatment step was not performed after performing the printing step and the dyeing step.

[Recording methods 10 to 12]
In the recording method 1, a printed matter was prepared in the same manner except that the heating temperatures in the heat treatment step were changed to 140 ° C., 220 ° C., and 250 ° C., respectively, and these were designated as recording methods 10 to 12.

[Recording methods 13 to 15]
In the recording method 1 described above, the application method of the urea aqueous solution, which is the urea aqueous solution in the dyeing process, is the spray coating device shown in FIG. 4 b), and the roller coating device provided with a sponge on the surface shown in FIG. A printed material was prepared in the same manner except that each of the extrusion coating apparatuses described in d) of FIG.

<Evaluation of printed materials>
The following evaluation was performed for each printed matter created by the above recording method.

[Evaluation of bleeding resistance]
The created solid images, thin line images, and white character images were visually observed for the occurrence of bleeding, and bleeding resistance was evaluated according to the following criteria to determine the average level of each color.

◎: There is no blur in the border area between the solid image and the white background, the thin line is not thick, and the drawability of the white character is clear. ○: There is no blur in the border area between the solid image and the white background, the thin line is not thick, and the white area is blank. Character drawability is slightly unclear, but there is no problem in quality. △: There is no blur in the border area between the solid image and the white background, but there is no thickening of the thin line and white characters cannot be recognized. ×: Solid image and the white background There is bleeding in the border area, and there is no thickening of fine lines, but there are bleeding along the fibers in less than 10 places, and white characters cannot be recognized. XX: The blurring is intense in the border area between the solid image and the white background, and the thin lines are thick. There are more than 10 spots along the fiber, and white characters cannot be recognized. [Evaluation of image density]
The density and unevenness of each color solid image prepared at a printing density of 100% were visually observed, the image density was evaluated according to the following criteria, and the average level of each color was determined.

A: Sufficient image density and no occurrence of unevenness. O: Sufficient image density but slight unevenness. Δ: Slightly low image density. X: Clearly low image density. : Image density is clearly low and generation of strong unevenness is also recognized. Table 1 shows the evaluation results obtained as described above.

  As is apparent from the results shown in Table 1, the image produced by the ink jet recording method defined in the present invention has a pudding and a product having a uniform and high image, in which the occurrence of bleeding is suppressed compared to the comparative example. You can see that

It is the schematic which shows an example of the provision method of the aqueous | water-based dye ink and urea aqueous solution using the inkjet head of a line head system. It is the schematic which shows another example of the provision method of the aqueous | water-based dye ink and urea aqueous solution using the inkjet head of a line head system. FIG. 3 is a bottom view of an ink jet head unit including the ink jet head that discharges the aqueous dye ink shown in FIG. 2 and a line head type ink jet head that discharges a urea aqueous solution. It is a schematic line figure which shows the flow of each process in the inkjet recording method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 Inkjet head 3 Spray coating device 4 Roller coating device 5, 7 Urea aqueous solution supply part 6 Extrusion coating device 8 Flat panel heater 9 Heating roller 10 Support roller A Printing process B Dyeing process C Heat treatment process D Cleaning process INK aqueous dye inks U urea solution _{H Y, H M, H C} , inkjet _{H K} ink head H _U urea solution for an inkjet head P fabric

Claims (2)

A water-soluble resin having an acid dye or a direct dye as a water-soluble dye, a carboxyl group or a sulfo group as an acid group, and an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less on a fabric having no ink receiving layer Ink jet, characterized in that after the water-based dye ink containing the ink is discharged and printed, urea is applied to the fabric in an amount of 1.0 g / m ² or more, and then the fabric is subjected to a heat treatment at a temperature of 150 ° C. or more. Recording method. 2. The ink jet recording method according to claim 1, wherein the fabric is heated to a temperature of 40 [deg.] C. or more when the water-based dye ink is discharged onto the fabric.

Images