JP2010070886A - Inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording method using an inkjet printing process by which the need of a pretreatment to a fabric is eliminated, and image bleeding is suppressed to provide a print with a high density. <P>SOLUTION: The inkjet recording method includes: jetting and printing an aqueous dye ink containing a reactive dye and a water-soluble resin having carboxy or sulfo group as acidic groups, and having an acid value of 70 mg KOH/g or more and 300 mg KOH/g or less on a fabric having no ink receiving layer; then applying 1.0 g/m<SP>2</SP>or more of urea and 0.005 mol/m<SP>2</SP>or more of an inorganic alkali to the fabric; and subsequently heat-treating the fabric at a temperature of 150°C or more. <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-based dye ink containing a reactive dye and a water-soluble resin having a carboxyl group or a sulfo group as an acidic 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 After discharging and printing, 1.0 g / m ² or more of urea and 0.005 mol / m ² or more of inorganic alkali are applied to the fabric, and then the fabric is heated at a temperature of 150 ° C. or more. An inkjet recording method characterized by the above.

  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 a reactive dye and a carboxyl group or a sulfo group as an acidic group in a fabric having no ink receiving layer, and has an acid value of 70 mgKOH / g or more, After discharging and printing a water-based dye ink containing a water-soluble resin of 300 mgKOH / g or less, 1.0 g / m ² or more of urea and 0.005 mol / m ² or more of inorganic alkali are applied to the fabric, Next, the inkjet recording method characterized in that the fabric is subjected to a heat treatment at a temperature of 150 ° C. or higher, so that no pre-treatment on the fabric is required, image bleeding is suppressed, and a high-density printed matter is obtained. It is up to the present invention that the method can be realized.

  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 coexisting inorganic alkali together with urea having deliquescence in the ink, the water and the ink environment necessary for the color development reaction are ensured, and high density image is achieved by high temperature color development at a temperature of 150 ° C. or higher. I was able to. Further, as defined in claim 2, preferably, when printing is performed, the fabric is heated to 40 ° C. or more to evaporate water in the ink that has landed on the fabric, thereby quickly concentrating the ink. It was possible to prevent image bleeding by increasing the viscosity.

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

<Water-based dye ink>
The water-based dye ink according to the present invention (hereinafter also simply referred to as ink) has at least a reactive dye, 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. And a resin.

(Reactive dye)
One feature of the ink according to the present invention is that a reactive dye is used as a coloring material. Preferably, in consideration of dyeability and fastness to the fabric, the reactive group type of the reactive dye is preferably a monochromatic triazine type.

  Examples of reactive 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.

  Specific examples of reactive dyes that can be applied to the ink according to the present invention are listed below, but the present invention is not limited to the reactive dyes exemplified above.

C. I. Reactive Yellow 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95, 102 , 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176,
C. I. Reactive Orange 1, 4, 5, 7, 11, 12, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91, 92 , 93, 95, 107,
C. I. Reactive Red2, 3, 3: 1, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66, 78 83, 84, 106, 111, 112, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180, 183, 184, 187, 190 , 193, 194, 195, 198, 218, 220, 222, 223, 226, 228, 235,
C. I. Reactive Violet 1, 2, 4, 5, 6, 22, 23, 33, 36, 38,
C. I. Reactive Blue 2, 3, 4, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77, 79 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191, 194 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236,
C. I. Reactive Green 8, 12, 15, 19, 21,
C. I. Reactive Brown 2, 7, 9, 10, 11, 17, 18, 19, 21, 23, 31, 37, 43, 46,
C. I. Reactive Black5, 8, 13, 14, 31, 34, 39 etc. are mentioned.

  The concentration of these reactive dyes in the ink is preferably 0.1 to 20% by mass, and more preferably 0.2 to 13% by mass. If it is less than 0.1% by mass, the concentration obtained is insufficient, and if it exceeds 20% by mass, the viscosity becomes too high and the injection becomes unstable.

(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.

  In order to achieve the object of the present invention, the water-soluble resin is preferably used in an amount of 2% by mass or more and 10% by mass or less, and preferably 3% by mass or more and 6% by mass or less. More preferred.

  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 addition to the reactive dye and water-soluble resin described above, various additives can be used in the ink according to the present invention as necessary.

(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, inorganic alkali agent>
In the inkjet recording method of the present invention, after applying the aqueous dye ink according to the present invention to a fabric, urea is applied to the fabric at 1.0 g / m ² or more and inorganic alkali is applied at 0.005 mol / m ² or more. It is characterized by that.

(urea)
In the ink jet recording method of the present invention, one feature is that urea is applied to an image-formed fabric in an amount of 1.0 g / m ² or more as a dyeing assistant for increasing the dyeing efficiency of the reactive dye on the fabric. And 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.

(Inorganic alkali)
In the ink jet recording method of the present invention, from the viewpoint of increasing the efficiency of dyeing of reactive dyes onto the fabric, it is preferable to apply 0.005 mol / m ² or more of inorganic alkali together with urea to the image-formed fabric. One feature is preferably 0.005 mol / m ² or more and 0.3 mol / m ² or less, and more preferably 0.005 mol / m ² or more and 0.1 mol / m ² or less.

  As for the adhesion amount of inorganic alkali, there are a method of adjusting and applying the concentration of inorganic alkali in the alkali-supplying ink containing urea, a method of adjusting the amount of application to the fabric, etc., whichever method is used. good. If the amount of adhered alkali is less than 0.01 mol, not only will the amount of alkali necessary for color development be insufficient, but the color density will be lowered, and the dark dyeing effect (aggregation effect) of the dye by the alkali will also be reduced, reducing the image density and blur suppression. Resulting in.

  As a reactive dyeing mechanism, dyeing efficiency can be enhanced by dyeing in an alkaline atmosphere. In particular, monochromatic triazine-based reactive dyes are often used, but as the reaction mechanism, dehydrochlorination reaction occurs with cellulose molecules and binds to the fibers, so this hydrochloric acid is neutralized by inorganic alkaline substances, and the reaction proceeds. Dyeing is promoted.

  The inorganic alkali is not particularly limited as long as the required amount of alkali can be supplied at the time of dyeing, and examples thereof include sodium silicate, caustic soda, caustic potash, sodium carbonate, sodium bicarbonate, potassium carbonate, and the like. Baking soda is preferred from the viewpoints of dyeability and storage stability.

  There is no restriction | limiting in particular as an application method to the fabric of the aqueous solution containing urea and an inorganic alkali, An inkjet head system, a coater system, a roller system, a spray system etc. can be selected suitably and used. Note that a specific method for providing them will be described later.

<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 reactive dye and a water-soluble resin according to the present invention is applied onto a cloth by an ink jet method, and at this time, the cloth is heated to 40 ° C. or more for printing, bleeding, etc. From the viewpoint of preventing
2) A dyeing step of applying a urea / alkali aqueous solution containing urea and an inorganic alkali 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 ink jet recording method of the present invention is not particularly limited as long as it contains fibers that can be dyed with reactive dyes. Among them, cotton, hemp, wool, silk Those containing fibers such as rayon and polyamide are preferred. Among them, it is particularly preferable that cotton and silk fibers are contained.

  As a medium for printing, the above-described fibers may be in any form such as woven fabric, knitted fabric, and non-woven fabric. Further, as a fabric that can be used in the present invention, it is preferable that the fiber that can be dyed with a reactive dye is 100%. However, a mixed woven fabric or a mixed non-woven fabric with polyester, acetate or the like is also used as a textile for printing. Can be used. Further, the thickness of the yarn constituting the fabric as described above is preferably in the range of 10 to 100d.

[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 for applying urea / alkaline aqueous solution]
In the ink jet recording method of the present invention, the application order of the aqueous dye ink and the aqueous solution containing urea and inorganic alkali at a predetermined concentration on the fabric is not particularly limited, but after the aqueous dye ink is applied on the fabric, When the ink is in a wet state, it is preferable to immediately apply an aqueous solution containing urea and inorganic alkali at a predetermined concentration to dye the reactive dye onto the fabric.

  The method of applying the urea / alkaline aqueous solution to the fabric holding the aqueous dye ink in a wet state is not particularly limited as long as it is a device that can uniformly supply a liquid, and the inkjet as described above. A head method, a coater method, a roller method, a spray method, or 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 a urea / alkali aqueous solution using a line head type ink jet head.

In FIG. 1 a), the line head type inkjet heads H _Y , H _M , H _C , and H _K that transport the fabric P from the top to the bottom and discharge the aqueous dye ink that covers the entire width of the fabric P. In addition, line head type inkjet heads _HUA that discharge aqueous solutions containing urea and inorganic alkali corresponding to each are arranged. On the fabric P being conveyed continuously, after discharging the water-based yellow dye ink from the ink jet head H _Y, discharging an aqueous solution immediately containing urea and inorganic alkaline ink-jet head H _UA, successively, water-based magenta dye ink and urea And an aqueous solution containing an inorganic alkali, an aqueous cyan dye ink and an aqueous solution containing urea and inorganic alkali, and an aqueous black dye ink and an aqueous solution containing urea and inorganic alkali 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. This is a configuration in which a line head type inkjet head _HUA is arranged, and either the configuration of a) of FIG. 1 or the configuration of b) of FIG. 1 may be used.

  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, line head type inkjet heads H _Y , H _M , H _C , and H _K that discharge aqueous dye ink and line head type inkjet heads H _UA that discharge an aqueous solution containing urea and inorganic alkali are: It is a line head type ink jet head unit in a bonded form.

  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 solution containing urea and inorganic alkali.

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 solution containing urea and inorganic alkali is disposed. The nozzles of the inkjet heads H _Y and H _UA 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 discharges a serial head type aqueous dye ink independently and an inkjet head that discharges an aqueous solution containing urea and inorganic alkali of the serial head type are arranged in parallel on the downstream side thereof, Alternatively, a serial head type ink jet recording method in which an ink jet head for ejecting aqueous dye ink is provided on a carriage and an ink jet head for ejecting an aqueous solution containing urea and inorganic alkali is disposed at both ends thereof can be used.

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

  Further, as a method for applying an aqueous solution containing urea and inorganic alkali, 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, and a blade coating apparatus. A bar coating device, a slide 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 reactive 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 where the washing is finished with water, but when fastness is required, washing with water, washing with water and soaping are effective. 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 a urea / alkali aqueous 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 water-based dye ink INK is discharged onto the fabric P, immediately after the dyeing process B, an aqueous solution UA containing urea and inorganic alkali is applied using the inkjet head 2.

  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.

  In FIG. 4 b), the spray coating apparatus 3 is used as means for applying the aqueous solution UA containing urea and inorganic alkali onto the fabric P, and the aqueous solution UA containing urea and inorganic alkali is sprayed onto the fabric P. Shows how to land.

  FIG. 4 c) shows a method of applying an aqueous solution UA containing urea and inorganic alkali 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 a resin-based sponge, and an aqueous solution containing urea and inorganic alkali is supplied to the roller coating device 4 from the aqueous solution supply unit 5 containing urea and inorganic alkali located at the top of the roller coating device 4. Is supplied to the sponge constituting the fabric and then re-supplied to the fabric.

  FIG. 4 d) shows a method of applying an aqueous solution UA containing urea and inorganic alkali to the fabric P using a quantitative 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 water-soluble dye inks of the following colors was prepared.

(Preparation of yellow ink 1)
C. I. Reactive Yellow 95 (RY95) 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. Instead of Reactive Yellow 95 (RY95), C.I. I. Magenta ink 1 was obtained in the same manner except that Reactive Red 24 (RR24) was used.

(Preparation of cyan ink 1)
In the preparation of the yellow ink 1, C.I. I. Instead of Reactive Yellow 95 (RY95), C.I. I. Cyan ink 1 was obtained in the same manner except that reactive blue 72 (RB72) was used.

(Preparation of black ink 1)
In the preparation of the yellow ink 1, C.I. I. Instead of Reactive Yellow 95 (RY95), C.I. I. A black ink 1 was obtained in the same manner except that reactive black 8 (RBk8) was used.

(Preparation of light magenta ink 1)
C. I. Reactive Red 24 (RR24) 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 Reactive Red 24 (RR24), C.I. I. A light cyan ink 1 was obtained in the same manner except that reactive blue 72 (RB72) 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 urea / inorganic alkaline aqueous solution (UA liquid) >>
[Preparation of UA liquid 1]
7.0g of urea
Sodium carbonate (0.028 mol) 3.0 g
Diethylene glycol monobutyl ether 8.0g
Diethylene glycol 23.0g
Glycerin 4.5g
Olfine E1010 (Nisshin Chemical Co., Ltd.) 5.3g
UA liquid 1 which is an aqueous solution containing urea carbonate and sodium carbonate as an inorganic alkali was prepared by adding ion-exchanged water to 100 ml as described above.

[Preparation of UA liquid 2]
In the preparation of the UA liquid 1, a UA liquid 2 was prepared in the same manner except that sodium carbonate (0.028 mol) was removed.

[Preparation of UA liquid 3]
In the preparation of the UA liquid 1, a UA liquid 3 was prepared in the same manner except that urea was removed.

[Preparation of UA solutions 4-6]
In the preparation of the UA liquid 1, UA liquids 4 to 6 were prepared in the same manner except that the addition amounts of urea were changed to 1.75 g, 3.5 g, and 17.5 g, respectively.

[Preparation of UA liquid 7]
In the preparation of UA liquid 1, UA liquid 7 was prepared in the same manner except that 1.12 g (0.028 mol) of sodium hydroxide was used instead of 3.0 g (0.028 mol) of sodium carbonate. did.

[Preparation of UA liquid 8]
In the preparation of UA liquid 1, UA liquid 8 was prepared in the same manner except that 1.57 g (0.028 mol) of potassium hydroxide was used instead of 3.0 g (0.028 mol) of sodium carbonate. did.

[Preparation of UA liquid 9]
In the preparation of the UA liquid 1, the UA liquid was prepared in the same manner except that 2.35 g (0.028 mol) of sodium hydrogen carbonate (bicarbonate) was used instead of 3.0 g (0.028 mol) of sodium carbonate. 9 was prepared.

[Preparation of UA solution 10]
In the preparation of the UA liquid 1, a UA liquid 10 was prepared in the same manner except that 3.86 g (0.028 mol) of potassium carbonate was used instead of 3.0 g (0.028 mol) of sodium carbonate. .

[Preparation of UA liquid 11]
In the preparation of the UA liquid 1, a UA liquid 11 was prepared in the same manner except that the amount of sodium carbonate added was changed to 1.11 g (0.0105 mol).

[Preparation of UA liquid 12]
In the preparation of the UA liquid 1, a UA liquid 12 was prepared in the same manner except that the amount of sodium carbonate added was changed to 1.86 g (0.0175 mol).

[Preparation of UA liquid 13]
In the preparation of the UA solution 1, a UA solution 13 was prepared in the same manner except that the amount of sodium carbonate added was changed to 7.5 g (0.07 mol).

[Preparation of UA liquid 14]
In the preparation of the UA liquid 1, a UA liquid 14 was prepared in the same manner except that the amount of sodium carbonate added was changed to 18.8 g (0.177 mol).

<Inkjet image recording>
[Recording method 1]
The ink set 1 prepared above, the configuration according to FIG. 2, FIG. 3, the inkjet head H _UA for discharging an aqueous solution further containing an ink jet head and urea and inorganic alkali for light magenta ink, and the ink jet head for cyan ink Each was loaded into a piezo-type inkjet head manufactured by Konica Minolta IJ Co., Ltd. equipped with an inkjet head _HUA that discharges an aqueous solution containing urea and inorganic alkali. 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%.

In addition, each ink-jet head _HUA was loaded with the UA liquid 1, and each color aqueous dye ink was discharged onto the fabric, and then immediately discharged. The discharge conditions were such that the application amount of urea was 2.0 g / m ² and the application amount of sodium carbonate as an inorganic alkaline agent was 0.008 mol / m ² . In addition, the used cloth used the cotton cloth which has not performed the pre-processing of the plain weave 20cm / P under processing which consists of 100% of cotton.

  Further, when each color aqueous dye ink and the UA liquid 1 were applied to the fabric, the fabric was heated so that the printing surface temperature of the fabric would be 50 ° C. by a flat panel heater disposed in the lower part of the fabric.

  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 methods 4 to 16]
In the recording method 1, in place of the UA liquid 1 which is an aqueous solution containing urea and inorganic alkali, UA liquids 2 to 16 were used, and the adhesion amount of urea and inorganic alkali was changed to the amount shown in Table 1. Similarly, printed materials were prepared and designated as recording methods 4 to 16.

[Recording method 17]
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.

[Recording method 18]
In the recording method 1, a printed matter was prepared in the same manner except that the heat treatment step was not performed after the printing step and the dyeing step, and this was designated as the recording method 18.

[Recording methods 19 to 21]
In the recording method 1, a printed matter was produced 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 19 to 21.

[Recording methods 22 to 24]
In the recording method 1, the application method of the UA liquid 1, which is an aqueous solution containing urea and inorganic alkali, in the dyeing step is applied to the surface of the spray coating apparatus shown in FIG. Printed materials were prepared in the same manner except that they were respectively changed to the roller coating device provided with a sponge and the extrusion coating device described in 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 application | coating method of the aqueous | water-based dye ink and urea / alkaline 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 / alkali 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 an aqueous solution containing urea and inorganic alkali. 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 Aqueous solution supply unit containing urea and inorganic alkali 6 Extrusion coating device 8 Flat panel heater 9 Heating roller 10 Support roller A Printing process B Dyeing process C Heating step D cleaning process iNK aqueous dye inks UA urea and an aqueous solution containing an inorganic alkaline _{H Y, H M, H C} , H K ink-jet head H inkjet heads P fabric for _UA lye

Claims (2)

A water-based dye ink containing a reactive dye and a water-soluble resin having a carboxyl group or a sulfo group as an acidic 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 After discharging and printing, 1.0 g / m ² or more of urea and 0.005 mol / m ² or more of inorganic alkali are applied to the fabric, and then the fabric is heated at a temperature of 150 ° C. or more. An inkjet recording method characterized by the above. 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