JP2006124855A - Deep color-processing method and ink jet printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ink jet printing method that has excellent deep color property, economic efficiency, conveying property, slip (weave twisting), fitness to the over-printing and excellent light stability. <P>SOLUTION: In this print dyeing, a fabric (for example, polyester fiber woven fabric having a refractive index of 1.6 to 1.7) is treated (printed) with deep color processing solution including a resin having a refractive index lower than that of the fabric (for example, a silicone resin with a refractive index of less than 1.4 ) to form an image-like pattern. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ink for inkjet printing, a recording method, and a recorded matter.

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

  Utilizing the advantages of the ink jet system, printing on a fabric, that is, a so-called ink jet textile image forming method (recording system) has been developed. Unlike conventional textile printing, inkjet textile printing does not require the creation of a plate and can quickly form an image with excellent gradation, so that delivery time can be shortened and small quantities can be produced. Furthermore, this is an image forming method that is environmentally superior because it requires only a required amount of ink as an image and therefore has little waste liquid.

  However, ink-jet printing has a disadvantage that the amount of color material adhering to the fabric is smaller than that of conventional printing such as screen printing, and therefore the image density is low. When the color material concentration in the ink is increased in order to increase the image density, the color material is precipitated and aggregated, and problems such as ejection failure and image quality degradation occur.

  Furthermore, synthetic fibers, particularly polyester, have a problem that the fiber surface has a high reflectance and it is difficult to obtain a dark color.

  Therefore, development of an ink jet printing method that increases or makes the image density high is strongly desired.

  Japanese Patent Laid-Open No. 2000-226780 discloses various additives such as a method in which a pretreatment agent contains paraffin wax or polyethylene oxide, and Japanese Patent Laid-Open No. 10-195576 discloses a method in which a polyoxolane resin is contained. The method of making it contain is disclosed (for example, refer patent documents 1-3).

  However, these methods not only provide a satisfactory density, but the pretreatment agent is applied to the front surface of the fabric by a pad-dry method or the like, so that it is also used for images that do not require a high density. Therefore, the waste of the additive increases the cost and the cleaning load.

  An image-like is a non-uniform, non-solid image, and can be realized by performing image formation launch while appropriately changing the density of the image by changing the amount of ink attached to the fabric.

  On the other hand, in the conventional textile printing, when it is necessary to make black appear blacker, so-called dark color processing is performed in which a resin or fine particle substance having a refractive index lower than that of the cloth is attached to the fiber surface to make it appear darker. However, a finishing process for dark color processing is required, resulting in a decrease in productivity and high cost. In addition, there are problems such as adhesion of foreign matter and contamination during the finishing process.

Further, since it is performed by the pad dry cure method or the like as in the pretreatment, the resin adheres to the entire fabric, so that there is a problem that slip (swing) easily occurs or overprinting is difficult.
Japanese Patent Laid-Open No. 5-18662 Japanese Patent Laid-Open No. 10-237776 JP 58-36280 A

  SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and its purpose is an inkjet printing method excellent in excellent darkness, economical efficiency, transportability: slip (shaking), suitability for overprinting, and light resistance. Is to provide.

  As a result of intensive studies in view of the above problems, it has been found that this can be achieved by the following method. The above object of the present invention is achieved by the following configurations.

(Claim 1)
In textile printing, a dark color processing liquid characterized by applying a dark color processing liquid containing a resin having a film forming ability having a refractive index lower than that of the fabric surface to an image recorded on the fabric with an ink having a color material. Method.

(Claim 2)
2. The dark color processing method according to claim 1, wherein the method of applying the dark color processing liquid is an ink jet method.

(Claim 3)
The image is a film in which ink is ejected onto a fabric by an ink jet method using an ink containing at least a coloring material, water, and a water-soluble organic solvent, and a refractive index lower than that of the fabric surface by the ink jet method. An ink-jet textile printing method characterized in that dark color processing is performed by applying a dark color processing liquid containing a resin having forming ability.

(Claim 4)
4. The ink jet printing method according to claim 3, wherein the viscosity of the resin having a film forming ability is 1 to 50 mPa · s when the concentration is 10%.

(Claim 5)
The inkjet printing method according to claim 3 or 4, wherein the dark color processing liquid contains water and a polyhydric alcohol.

(Claim 6)
The inkjet printing method according to any one of claims 3 to 5, wherein a refractive index of the resin having the film forming ability is 0.1 or more lower than that of the fabric.

(Claim 7)
The ink-jet printing method according to any one of claims 3 to 6, wherein the dark color processing liquid contains a light fastness improver.

(Claim 8)
The ink-jet printing method according to any one of claims 3 to 7, wherein the resin having a film forming ability is a silicon-based resin.

(Claim 9)
The ink-jet printing method according to claim 3, wherein the color material is a disperse dye.

(Claim 10)
The inkjet textile printing method according to any one of claims 3 to 9, wherein the fabric is polyester.

  According to the ink jet textile printing method of the present invention, it is possible to provide an ink jet textile image forming method (recording method) excellent in darkness, economy, and transportability: slip (blurring) and light resistance.

  Hereinafter, the best mode for carrying out the present invention will be described in detail. The present invention is not limited to these.

  First, the dark color processing liquid used in the ink jet textile printing method of the present invention will be described. The dark color processing liquid of the present invention contains a resin having a refractive index lower than that of the fabric and having a film forming ability, water, and a water-soluble organic solvent. Examples of the resin having a film forming ability that is preferably used include, for example, a block of propylene oxide and ethylene oxide, or a urethane-based resin composed of a random copolymer polyether diol and hexamethylene diisocyanate, polypentadecafluorooctyl acrylate, polytetrafluoroethylene, poly Examples thereof include fluorine resins such as trifluoroethyl acrylate, silicon resins such as polydimethylsilane, polymethylhydrosiloxane siloxane, and polydimethylsiloxane, and acrylate resins such as polyethyl acrylate and polyethyl methacrylate.

  The refractive index of the polyester fiber is about 1.6 to 1.7, and 1.5 or less is preferable for producing the effect of darkening, and a silicone resin having a low refractive index of 1.4 or less is particularly preferable. Furthermore, you may use a crosslinking agent and a catalyst as needed. The resin can also be contained as an emulsion in the dark color processing liquid.

  The water used in the dark color processing liquid is pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water.

  In addition, a water-soluble organic solvent is contained for the purpose of preventing clogging.

  Examples of main water-soluble organic solvents include polyhydric alcohols (for example, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene glycol, triethylene glycol, tripropylene Glycol, 1,2,4-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 1,2-hexanediol, 1,5-pentanediol, 1,2-pentanediol 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,3-butanediol, 2-methyl -1,3-propanediol, etc.), amines (for example, , Ethanolamine, 2- (dimethylamino) ethanol, etc.), monohydric alcohols (eg, methanol, ethanol, butanol, etc.), alkyl ethers of polyhydric alcohols (eg, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl) Ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.), 2,2'-thiodiethanol, amides (for example, N, N-dimethylformamide etc.), heterocyclic rings (2-pyrrolidone etc.), acetonitrile etc. That. Polyhydric alcohol is particularly preferable.

  The dark color processing liquid preferably has a solid content concentration of 0.01 to 80% by mass and 0.1 to 50% by mass from the viewpoint of quick drying and film-forming properties of the resin capable of forming the film. It is particularly preferred.

  The dark color processing liquid contains 30 to 90% by mass of water, preferably 40 to 80% by mass, and 10 to 70% by mass, preferably 20 to 60% by mass of a water-soluble organic solvent. In addition, an antiseptic and an antifungal agent may be added for long-term storage stability. Examples of the antiseptic and antifungal agent include aromatic halogen compounds, methylene dithiocyanates, halogen-containing nitrogen-sulfur compounds, 1,2- Examples thereof include benzisothiazoline-3-one.

  Furthermore, it is preferable to contain a light resistance improver from the viewpoint of improving the light resistance of the recorded matter.

  The light fastness improver is not particularly limited as long as it has an action of suppressing discoloration of a recorded image due to ultraviolet light or visible light, and preferably a hindered amine light stabilizer (HALS), an ultraviolet absorber, and an antioxidant. 1 type (s) or 2 or more types chosen from the group which consists of an agent and a quencher (quenching agent) are mentioned.

  Examples of the ultraviolet absorber include benzophenone compounds, salicylate compounds, benzotriazole compounds, cyanoacrylate compounds, and metal oxides such as titanium oxide, zinc oxide, selenium oxide, and cerium oxide.

  Examples of the antioxidant include phenols such as hindered phenols, chromanes, clamans, hydroquinone derivatives, benzotriazoles (those that do not have ultraviolet absorbing ability), spiroindanes, and the like.

  Examples of the quencher include inorganic metal complexes such as nickel and cobalt. Among these, in particular, water-soluble HALS, benzotriazole-based compounds "including those having ultraviolet absorbing ability (used as ultraviolet absorbers and those not having this)" and phenolic antioxidants are used. preferable.

  The light resistance improver is preferably contained in the dark color processing liquid in an amount of 0.01 to 30% by mass, more preferably 0.1 to 20% by mass.

  The dark color processing liquid preferably has a viscosity at 20 ° C. of 20 mPas or less from the viewpoint of ejection stability. Therefore, the viscosity of the film-forming resin is preferably 1 to 50 mPa · s when the resin concentration is 10%.

  From the same viewpoint, the dark color processing liquid preferably has a surface tension of 20 to 70 mN / m, and more preferably 20 to 60 mN / m. Examples of a method for adjusting the surface tension within the range include addition of a surfactant and an organic solvent.

  Next, the ink used in the ink jet textile printing method of the present invention will be described, but it is the same as the ink used in ordinary ink jet textile printing.

  The inkjet ink of the present invention is a dye ink, a dispersed dye ink or a pigment ink.

Disperse dye ink and pigment ink are preferably used in the present invention, and disperse dye ink is particularly preferably used. Examples of the water-soluble dye used in the present invention include acidic dyes and reactive dyes. Specific compounds include
<Acid dye>
C. I. Acid Yellow 2, 3, 7, 17, 19, 23, 25, 29, 38, 42, 49, 59, 61, 72, 99
C. I. Acid Orange 56, 64
C. I. Acid Red 1, 8, 14, 18, 26, 32, 37, 42, 52, 57, 72, 74, 80, 87, 115, 119, 131, 133, 134, 143, 154, 186, 249, 254, 256
C. I. Acid Violet 11, 34, 75
C. I. Acid Blue 1, 7, 9, 29, 87, 126, 138, 171, 175, 183, 234, 236, 249
C. I. Acid Green 9, 12, 19, 27, 41
C. I. Acid Black 1, 2, 7, 24, 26, 48, 52, 58, 60, 94, 107, 109, 110, 119, 131, 155
<Reactive dyestuff>
C. I. Reactive Yellow 1, 2, 3, 13, 14, 15, 17, 37, 42, 76, 95, 168, 175
C. I. Reactive Red 2, 6, 11, 21, 22, 23, 24, 33, 45, 111, 112, 114, 180, 218, 226, 228, 235
C. I. Reactive Blue 7, 14, 15, 18, 19, 21, 25, 38, 49, 72, 77, 176, 203, 220, 230, 235
C. I. Reactive Orange 5, 12, 13, 35, 95
C. I. Reactive Brown 7, 11, 33, 37, 46
C. I. Reactive Green 8, 19
C. I. Reactive violet 2, 4, 6, 8, 21, 22, 25
C. I. Reactive Black 5, 8, 31, 39
Etc.

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

  As the pigment, known inorganic pigments, organic pigments, disperse dyes and the like can be used.

  Examples of organic pigments include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments. Polycyclic pigments such as pigments, dye lakes such as basic dye type lakes and acid dye type lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, and inorganic pigments such as carbon black Can be mentioned.

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

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

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

  The color material content is preferably 3 to 20% by mass, and more preferably 5 to 13% by mass.

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

  Examples of the dispersant preferably used in the disperse dye ink of the present invention include, for example, formalin condensate of sodium creosote oil sulfonate (eg, Demol C), formalin condensation of sodium cresolsulfonate and sodium 2-naphthol-6-sulfonate. , Formalin condensate of sodium cresol sulfonate, formalin condensate of sodium phenol sulfonate, formalin condensate of sodium β-naphthol sulfonate, sodium β-naphthalene sulfonate (eg Demol N) and sodium β-naphthol sulfonate Formalin condensate, lignin sulfonate (for example, Vanillex RN), sodium paraffin sulfonate (for example, Efcol 214), copolymer of α-olefin and maleic anhydride (for example, Florene G-70) ), Among others lignosulfonate salts.

  Dispersions preferably used for pigment ink include styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-maleic acid copolymer, styrene-maleic acid-acrylic acid alkyl ester copolymer Styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer Etc.

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

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

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

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

  The average particle diameter can be determined by a commercially available particle size measuring instrument using a light scattering method, an electrophoresis method, a laser Doppler method or the like. Specific examples of the particle diameter measuring apparatus include Zetar Sizer 1000 manufactured by Malvern.

  Moreover, an additive can be used for various performance improvement. As the additive, known antiseptics, antifungal agents, viscosity modifiers, metal chelating agents, antioxidants, ultraviolet absorbers and the like can be used.

  For the long-term storage stability of the ink, preservatives and antifungal agents may be added. As preservatives and antifungal agents, aromatic halogen compounds, methylene dithiocyanates, halogen-containing nitrogen sulfur compounds, 1,2- Examples include benzisothiazolin-3-one, but the present invention is not limited thereto.

  Pigment or disperse dye ink is dispersed in an aqueous dispersion medium at a high concentration by a dispersing device such as a ball mill, a sand mill, a roll mill, a speed line mill, a homomixer or a sand grinder, and the obtained aqueous dispersion is 1 to 10 times. It can be manufactured by diluting to a certain extent, further adding various additives to make ink, deaeration treatment, and filtration.

  In order to obtain a high-definition image, recording is preferably performed using an inkjet head having a nozzle diameter of 10 μm to 50 μm. 50 μm or less is preferable from the graininess, and 10 μm or more is preferable because the droplet volume becomes too small and is affected by airflow.

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

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

As the water-soluble metal salt, an inorganic salt such as an alkali metal such as KCl or CaCl ₂ or an alkaline earth metal, an organic acid salt, or the like can be used.

  As the polycation compound, polymers or oligomers of various quaternary ammonium salts, polyamine salts, and the like can be used.

  Some water-soluble metal salts and polycation compounds change the color tone of the dyed product or reduce the light fastness, and therefore are preferably selected according to the target dyed product.

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

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

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

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

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

  In addition, a dyeing assistant can be added to the fabric. The dyeing assistant produces an eutectic compound with water aggregated on the fabric when steaming the printed fabric, and has the effect of reducing the amount of moisture that re-evaporates and shortening the heating time. Further, this eutectic compound has a function of dissolving the dye on the fiber and promoting the diffusion rate of the dye into the fiber. Urea is mentioned as a dyeing assistant.

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

  In the ink jet textile printing method for printing on a fabric, it is desirable to wind up the printed fabric after the ink is emitted, to develop a color by heating, and to wash and dry the fabric. In ink jet textile printing, after ink is printed on a cloth, it is not dyed well just by leaving it alone. Further, when printing on a long fabric for a long time, the fabric comes out endlessly, so that the fabric printed on the floor or the like overlaps and takes a place. Furthermore, it is unsafe and may get dirty unexpectedly. Therefore, an operation of winding after printing is necessary. During this operation, a medium that is not related to printing, such as paper, cloth, or vinyl, may be sandwiched between the cloth and the cloth. However, it is not always necessary to wind up when cutting in the middle or short fabric.

  The printed fabric may be immediately heat-treated or may be heat-treated after a while, and may be dried and colored according to the intended use. As the heat treatment method, a method suitable for the application, such as an oven, a heat roll, or steam, may be selected.

  Cleaning is necessary after the heat treatment. This is because the dye stability that is not involved in the dyeing remains, so that the color stability is deteriorated and the fastness is lowered. It is also necessary to remove the pretreatment product applied to the fabric. If left as it is, the fabric is dyed as well as a decrease in fastness. Therefore, it is necessary to perform cleaning according to the object to be removed and the purpose.

  Drying is required after washing. After the washed fabric is squeezed or dehydrated, it is dried or dried using a dryer, heat roll, iron or the like.

  In addition, in the case of the inkjet printing method of the present invention, in order to obtain a uniform dyed product, natural impurities (oil, fat, wax, pectin, natural pigment, etc.) adhering to the fabric fiber before pre-treating the ink receiving layer on the fabric ), It is desirable to wash away residues (such as glue) and dirt used in the fabric manufacturing process. As cleaning agents used for cleaning, alkalis such as sodium hydroxide and sodium carbonate, surfactants such as anionic surfactants and nonionic surfactants, enzymes and the like are used.

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

  Hereinafter, the present invention will be specifically described with reference to examples.

Example 1
<Preparation of dispersed ink>
[Adjustment of dark color machining fluid]
Polon MF-14 3 parts (amino-modified silicone, effective 15%, manufactured by Shin-Etsu Chemical Co., Ltd.)
Ethylene glycol 20 parts Glycerin 10 parts Proxel GXL (D) (manufactured by Avicia Co., Ltd.) 0.01 parts Ion-exchanged water 69 parts [Ink adjustment]
[Adjustment of yellow ink]
The following mixture was dispersed using a sand grinder. Dispersion was stopped when the average particle size reached 160 nm to obtain Dispersion-1. The particle size was measured by the scattering intensity of Malter Zeta Sizer 1000.

Commercial C.I. I. Disperse Yellow 149 30 parts Glycerin 20 parts Ion-exchanged water 35 parts Lignin sulfonate sodium (Vanilex RN Nippon Paper Industries Co., Ltd.) 15 parts Further mixed with the following ingredients, filtered through a 0.3 μm membrane filter, and further hollow fiber membrane module Degassing treatment was performed at 10 kPa or less (SEPAREL PF-004D manufactured by Dainippon Ink and Chemicals, Inc.), and the ink cartridge was filled to obtain a yellow ink.

Dispersion-1 20 parts Ethylene glycol 20 parts Glycerin 10 parts Proxel GXL (D) (manufactured by Avicia Co., Ltd.) 0.01 parts Ion-exchanged water 50 parts [Adjustment of magenta ink]
The following mixed solution was dispersed in the same manner as in the preparation of Dispersion-1 to obtain Dispersion-2.

Commercial C.I. I. Disperse Red 302 30 parts Glycerin 20 parts Ion-exchanged water 35 parts Lignin sulfonate sodium (Vanilex RN Nippon Paper Industries Co., Ltd.) 15 parts Further, the following components were mixed to prepare a magenta ink in the same manner as the yellow ink.

Dispersion liquid-2 20 parts Ethylene glycol 20 parts Glycerin 10 parts Proxel GXL (D) (manufactured by Avicia Co., Ltd.) 0.01 part Ion-exchanged water 50 parts [Adjustment of cyan ink]
The following mixture was dispersed using a sand grinder. Dispersion was stopped when the average particle size reached 180 nm to obtain Dispersion-3.

Commercial C.I. I. Disperse Blue 60 30 parts Glycerin 20 parts Ion-exchanged water 35 parts Creosote oil sodium sulfonate (Demol C Kao Co., Ltd.) 15 parts The following components were mixed and filtered through a 0.3 μm membrane filter to obtain a cyan ink.

Dispersion-3 20 parts Ethylene glycol 20 parts Glycerin 10 parts Proxel GXL (D) (manufactured by Avicia Co., Ltd.) 0.01 part Ion-exchanged water 50 parts [Adjustment of black ink]
The following mixture was dispersed using a sand grinder. Dispersion was stopped when the average particle size reached 180 nm, and Dispersion-4 was obtained.

Commercial C.I. I. Disperse Orange 30 30 parts Glycerin 20 parts Ion-exchanged water 35 parts Creosote oil sodium sulfonate (Demol C Kao Co., Ltd.) 15 parts The following mixture was dispersed using a sand grinder. Dispersion was stopped when the average particle size reached 180 nm, and Dispersion-5 was obtained.

Commercial C.I. I. Disperse Violet 57 30 parts Glycerin 20 parts Ion exchange water 35 parts Sodium lignin sulfonate (Vanilex RN Nippon Paper Industries Co., Ltd.) 15 parts The following components were mixed and filtered through a 0.3 μm membrane filter to obtain a black ink.

Dispersion-3 10 parts Dispersion-4 25 parts Dispersion-5 25 parts Ethylene glycol 20 parts Glycerin 5 parts Proxel GXL (D) (manufactured by Avicia Co., Ltd.) 0.01 part Ion-exchanged water 15 parts [Pretreatment of fabric ]
A woven fabric having 100% polyester fiber and a thread thickness of 50d was previously immersed in a pretreatment agent (polymer cation compound and guar gum), squeezed and dried.

[Create inkjet recording image]
The pre-treated polyester fabric in which the deep color processing liquid-1 obtained above and yellow, magenta, cyan, and black inks are mounted on an inkjet printer (Nassenger KS-1600, manufactured by Konica Minolta Technology Center Co., Ltd.). Color inks were ejected to create yellow, magenta, cyan, and black single color patches.

  Subsequently, the dark color processing liquid was discharged onto the color patch. The yellow patch was used for overprint suitability evaluation, and the dark color processing liquid was not discharged.

  Subsequently, the printed fabric was heat-treated at 180 ° C. for 10 minutes, washed with water and dried.

<Evaluation>
[Evaluation of inkjet recording image]
Each image-formed sample prepared as described above was evaluated for darkening effect and light resistance by the following method. [Evaluation of darkening effect]
The recorded image was allowed to stand for 1 day in an environment of 20 ° C. and 50% humidity, and then the L value was measured using an Xrite-938 Spectrodensitometer (manufactured by X-Rite). The measurement conditions were a D50 light source and a 2 ° field of view. Smaller L value indicates lower brightness and darker color [Evaluation of light fastness]
The image after recording is performed with xenon arc (JIS L O843) and judged on a blue scale (1st to 8th grades).
◎: Grade 8 ○: Grade 7 Δ: Grade 6 ×: Grade 5 or less [Evaluation of transportability]
The above-described fabric slip at the time of creating a recorded image was visually evaluated according to the following evaluation criteria.
○: No slip (visit) △: Slip, (visit) slightly seen ×: Slip, (visit) meandering severe [Overprint evaluation]
Black ink was further discharged onto the yellow patch, and the overprint state was visually confirmed according to the following evaluation criteria.
○: Good Δ: Good to inferior ×: Inferior Example 2
In Example 1, a recorded image was obtained in the same manner as in Example 1 except that instead of the dark color processing liquid-1, dark color processing liquid-2 having the following composition was used.

[Adjustment of dark color machining fluid]
Polon MF-14D 3 parts (Amino-modified silicone, 33% effective, Shin-Etsu Chemical Co., Ltd.)
Ethylene glycol 20 parts Glycerin 10 parts Proxel GXL (D) 0.01 part Ion-exchanged water 69 parts A recorded image was prepared and evaluated in the same manner as in Example 1. Example 3
[Adjustment of dark color machining fluid]
Polon MF-14D 3 parts (Amino-modified silicone, 33% effective, Shin-Etsu Chemical Co., Ltd.)
Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 part Ethylene glycol 20 parts Glycerin 10 parts Proxel GXL (D) 0.01 part Ion-exchanged water 69 parts << Comparative Example >>
Comparative Example 1
Four-color single-color patches were prepared in the same manner as in Example 1 except that the dark color processing liquid was not used, and evaluation was performed in the same manner as in Example 1.

Comparative Example 2
After preparing four-color single-color patches in the same manner as in Comparative Example 1, a darkening solution containing the following composition was darkened by a pad-dry method to obtain a fabric. Evaluation was performed in the same manner as in Example 1.

[Preparation of dark working fluid]
Polon MF-14D 3 parts (Amino-modified silicone, 33% effective, Shin-Etsu Chemical Co., Ltd.)
97 parts of ion-exchanged water are shown in Table 1.

Claims (10)

In textile printing, a dark color processing liquid characterized by applying a dark color processing liquid containing a resin having a film forming ability having a refractive index lower than that of the fabric surface to an image recorded on the fabric with an ink having a color material. Method. 2. The dark color processing method according to claim 1, wherein the method of applying the dark color processing liquid is an ink jet method. The image is a film in which ink is ejected onto a fabric by an ink jet method using an ink containing at least a coloring material, water, and a water-soluble organic solvent, and a refractive index lower than that of the fabric surface by the ink jet method. An ink-jet textile printing method characterized in that dark color processing is performed by applying a dark color processing liquid containing a resin having forming ability. 4. The ink jet printing method according to claim 3, wherein the viscosity of the resin having a film forming ability is 1 to 50 mPa · s when the concentration is 10%. The inkjet printing method according to claim 3 or 4, wherein the dark color processing liquid contains water and a polyhydric alcohol. The inkjet printing method according to any one of claims 3 to 5, wherein a refractive index of the resin having the film forming ability is 0.1 or more lower than that of the fabric. The ink-jet printing method according to any one of claims 3 to 6, wherein the dark color processing liquid contains a light fastness improver. The ink-jet printing method according to any one of claims 3 to 7, wherein the resin having a film forming ability is a silicon-based resin. The ink-jet printing method according to claim 3, wherein the color material is a disperse dye. The inkjet textile printing method according to any one of claims 3 to 9, wherein the fabric is polyester.