JP2019085577A - Inkjet printing method - Google Patents

Abstract

To provide an ink set for inkjet printing that can form an image excellent in fastness and light resistance to not only silk but also nylon or wool and additionally to a mixed spinning fabric of silk or nylon with urethane, assures a wide color reproduction range and has good storage stability.SOLUTION: An ink set for inkjet printing comprises yellow ink containing C.I. Acid Yellow 79, magenta ink containing at least one kind selected from the group consisting of C.I. Acid Red 138 and C.I. Acid Red 289, cyan ink containing C.I. Direct Blue 87, orange ink containing at least one kind selected from the group consisting of C.I. Acid Orange 33 and C.I. Acid Orange 94, blue ink containing at least one kind selected from the group consisting of C.I. Acid Blue 112 and C.I. Acid Blue 140 and black ink containing C.I. Acid Black 172.SELECTED DRAWING: None

Description

  The present invention relates to an ink set for ink jet textile printing comprising at least six colors of yellow ink, magenta ink, cyan ink, orange ink, blue ink and black ink, and an ink jet textile printing method using the ink set.

  Conventionally, screen printing method, roller printing method, rotary screen printing method, transfer printing method or the like is used as a method of printing an image on a fabric or the like. However, since it is necessary to prepare expensive screen frame, engraving roller, transfer paper, etc. for every change of image design, it is unsuitable for the cost in high-mix low-volume production, and responds quickly to diversification of fashion. It was difficult.

  In order to solve the drawbacks of the conventional textile printing method, a technique (hereinafter, also referred to as “ink-jet textile printing”) has been developed in which a sample is read by a scanner, image processing is performed by a computer, and the result is printed by an inkjet recording method. It is done. The inkjet recording method is a recording method in which ink droplets are ejected from an ink head toward a recording medium (for example, paper or fabric) and the droplets are adhered to the recording medium, and the mechanism is relatively simple and inexpensive. It is possible to form a high definition and high definition image. By applying such an ink jet recording method, it is not necessary to prepare a plate required by the conventional textile printing method, and an image having excellent gradation can be formed quickly, so that the delivery time can be shortened, and a large variety and small quantity production. There is an advantage that it is possible to cope with the situation. Moreover, according to the ink jet printing, since only the necessary amount of ink is used at the time of image formation, it has an environmental advantage such as less waste liquid as compared with the conventional screen printing and the like.

  By the way, when various dyes are used for ink jet printing, in addition to the performance such as color tone and fastness which are the criteria for selecting dyes for conventional printing, performances such as wide color reproduction range can be secured and storage stability is excellent. Is required. From the viewpoint of storage stability, for example, when changes in physical properties (for example, viscosity) or precipitation of solid content occur during ink storage, clogging of nozzles or ink discharge stability tends to be impaired.

  From such a point of view, an ink set for six-color ink jet printing having a wide color reproduction area and excellent in the fastness of the formed image and the storage stability of the ink can be obtained by appropriately selecting the colorant for the ink. It is proposed (for example, refer patent document 1). In Patent Document 1, C.I. I. Yellow ink containing acid yellow 79, C.I. I. Magenta ink containing Acid Red 249, C.I. I. Cyan ink containing direct blue 87, C.I. I. Black ink containing Acid Black 52: 1, C.I. I. Orange ink containing Acid Orange 95, and C.I. I. An ink set for ink jet printing comprising a blue ink containing Acid Blue 112 is disclosed.

Unexamined-Japanese-Patent No. 2007-238741

However, the ink set for ink jet printing disclosed in Patent Document 1 includes C.I. I. There is a problem that the light fastness and fastness of Acid Orange 95 are insufficient, and the light fastness and fastness of the image formed as a result are not very good. In particular, C.I. I. The fastness (dyeability) to acid black 52: 1 non-silk nylon and wool, and further to a blend fabric of silk and nylon and urethane was insufficient. Although the color reproduction range is improved to some extent, there is room for further improvement. As described above, the ink set for ink jet textile printing disclosed in Patent Document 1 has insufficient performance as an ink set and is poorly balanced.

  Therefore, some aspects according to the present invention are excellent in the fastness and light resistance to not only silk but also nylon and wool, and further a blend fabric of silk or nylon and urethane by solving at least a part of the above-mentioned problems. It is an object of the present invention to provide an ink set for ink jet textile printing which can form an image, secure a wide color reproduction area, and have excellent storage stability.

  The present invention has been made to solve at least a part of the problems described above, and can be realized as the following aspects or application examples.

Application Example 1
One aspect of the ink set for ink jet textile printing according to the present invention is
As a colorant, C.I. I. Yellow ink containing Acid Yellow 79,
As a colorant, C.I. I. Acid Red 138 and C.I. I. Magenta ink containing at least one selected from the group consisting of Acid Red 289;
As a colorant, C.I. I. Cyan ink containing Direct Blue 87,
As a colorant, C.I. I. Acid Orange 33 and C.I. I. An orange ink containing at least one selected from the group consisting of Acid Orange 94;
As a colorant, C.I. I. Acid Blue 112 and C.I. I. Blue ink containing at least one selected from the group consisting of Acid Blue 140;
As a colorant, C.I. I. Black ink containing acid black 172,
And the like.

  According to the ink set for ink jet printing of Application Example 1, the ink set for six colors containing a specific coloring agent is not only silk but also fast against not only silk but also nylon and wool, and further a blend of silk and nylon and urethane. While being able to form the image excellent in property and light resistance, a wide color reproduction range can be ensured and storage stability becomes favorable.

Application Example 2
In the ink set for inkjet textile printing of application example 1,
Each of the inks can contain 50% by mass or more of the acid dye contained as the colorant when the total amount of the colorant is 100% by mass.

  According to the ink set for inkjet textile printing of application example 2, an image excellent in fastness and light resistance can be formed more reliably, and a wide color reproduction area can be secured.

Application Example 3
In the ink set for ink jet textile printing of application example 1 or application example 2,
In at least one of the respective inks, C.I. I. Acid Violet 48 and C.I. I. It can further contain at least one selected from the group consisting of Acid Violet 97.

According to the ink set for inkjet textile printing of application example 3, it is possible to adjust the color tone of magenta or blue to a desired color tone. Therefore, C.I. I. Acid Violet 48
And C. I. Acid violet 97 is preferably added to the magenta ink or the blue ink.

Application Example 4
In the ink set for ink jet textile printing according to any one of application examples 1 to 3, the zinc content of each of the inks may be 50 ppm or less.

  According to the ink set for ink jet textile printing of application example 4, the storage stability of the ink can be further improved. In particular, C.I. I. When by-products and zinc ions produced in the process of producing the acid black 172 are present, a phenomenon occurs in which the viscosity of the ink increases with time. When the zinc content in the black ink is 50 ppm or less, the viscosity of the ink can be prevented from increasing with time.

Application Example 5
One aspect of the ink jet textile printing method according to the present invention is
An inkjet printing step of depositing ink on one side of a fabric using the ink set for inkjet printing of any one of Application Examples 1 to 4;
A cloth surface treatment step of causing a penetrant to adhere to the surface of the cloth to which the ink is attached;
It is characterized by including.

  According to the ink jet printing method of application example 5, an image having excellent fastness and light resistance can be formed on various fabrics. Further, by causing the penetrant to adhere to the fabric, after the ink soaks in the thickness direction of the fabric, it is possible to impart a penetrant effect to the fabric by the penetrant. Thereby, penetration in the lateral direction of the fabric is suppressed, and ink bleeding can be reduced.

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below is an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications implemented within the scope of the present invention.

1. Ink set for ink jet textile printing The ink set for ink jet textile printing according to the present embodiment (hereinafter, also simply referred to as “ink set”) contains C.I. I. Acid Yellow 79-containing yellow ink, and C.I. I. Acid Red 138 and C.I. I. Acid red 289, a magenta ink containing at least one selected from the group consisting of C.I. I. Cyan ink containing Direct Blue 87, and C.I. I. Acid Orange 33 and C.I. I. Acid Orange 94, an orange ink containing at least one selected from the group consisting of C.I. I. Acid Blue 112 and C.I. I. Acid Blue 140, a blue ink containing at least one selected from the group consisting of C.I. I. And black ink containing acid black 172. Thus, an image having excellent fastness and light resistance to not only silk but also nylon and wool, and further a mixture of silk and nylon and urethane by setting it as a six-color ink set containing a specific coloring agent As a result, a wide color reproduction area can be secured, and storage stability becomes good.

  Each color ink constituting the ink set according to the present embodiment contains a colorant, a moisturizer, a penetrant, water, and other additives. The components contained in each color ink will be described below.

1.1. Colorant The ink of each color constituting the ink set according to the present embodiment can form an image excellent in fastness and light resistance to not only silk but also nylon and wool, and further a blend fabric of silk or nylon and urethane. From the viewpoint of securing a wide color reproduction range, a specific acid dye as a colorant, that is, C.I. I. Acid Yellow 79, C.I. I. Acid Red 138 and C.I. I. Acid Red 289, at least one acid dye selected from the group consisting of C.I. I. Direct Blue 87, C.I. I. Acid Orange 33 and C.I. I. Acid Orange 94, at least one acid dye selected from the group consisting of C.I. I. Acid Blue 112 and C.I. I. Acid Blue 140, at least one acid dye selected from the group consisting of C.I. I. It is characterized in that it contains acid black 172. The ink set according to the present embodiment is used as an acid from the viewpoint of color mixing with two or more colors of ink to secure a wide color reproduction area and forming an image excellent in fastness and light resistance to various fabrics. Special compatibility is required between dyes. Therefore, it is necessary to use an acid dye composition as defined in the present embodiment, and at least six ink sets.

  Each color ink constituting the ink set according to the present embodiment may be composed of only the acid dye defined above as a colorant, but other colorants may be used in combination as long as the effects of the present invention are not impaired. can do. In each color ink, when the total amount of colorants is 100% by mass, the content ratio of the acid dye specified above is preferably 50% by mass or more, and more preferably 70% by mass or more.

  In each color ink constituting the ink set according to the present embodiment, the content of the coloring agent in the ink is from the viewpoint of obtaining sufficient color forming property of the image to be formed and the viewpoint of discharge stability from the head and storage stability And 1% by mass or more and 10% by mass or less, and more preferably 2% by mass or more and 7% by mass or less.

  The ink set according to the present embodiment is C.I. I. Acid Orange 33 and C.I. I. One of the characteristics is that the orange ink contains at least one acid dye selected from the group consisting of Acid Orange 94. A conventional ink set for ink jet printing comprises C.I. I. An orange ink containing Acid Orange 95 was used. C. I. Since the acid orange 95 is weak in light resistance, the formed image is also drawn to it and the light resistance is not so good. Further, the ink set according to the present embodiment is C.I. I. One feature is that the black ink containing the acid black 172 is provided. A conventional ink set for ink jet printing comprises C.I. I. A black ink containing Acid Black 52: 1 was used. Conventional C.I. I. The image formed using Acid Black 52: 1 is insufficient in fastness (dying), and in particular, fastness to nylon and wool other than silk, and further to a mixture of silk and nylon and urethane. It was enough. The ink set according to the present embodiment is C.I. I. Acid Orange 33 and C.I. I. An orange ink containing Acid Orange 94, C.I. I. By providing the black ink containing the acid black 172, it has become possible to form an image excellent in fastness and light resistance on various fabrics.

  Further, the ink set according to the present embodiment is C.I. I. Acid Blue 112 and C.I. I. There is also one feature in that a blue ink containing at least one acid dye selected from the group consisting of Acid Blue 140 is provided. By providing a blue ink containing these acid dyes, a wider color reproduction area can be secured, and an image having excellent fastness to various fabrics can be formed.

In each color ink constituting the ink set according to the present embodiment, C.I. I. Acid Violet 48 and C.I. I. It can further contain at least one selected from the group consisting of Acid Violet 97. Thereby, the color tone of magenta and blue can be adjusted to a desired color tone.

  Specific examples of toning are shown below.

  C.1 which may be included in magenta ink I. Acid Red 289 has a wide color reproduction range but has a property that the fastness is somewhat low. On the other hand, C.I. I. Acid Red 138 has a color reproduction area of C.I. I. Although slightly narrower than Acid Red 289, it has the property of high robustness. And C.I. I. Acid Red 289 and C.I. I. The color tone of Acid Red 138 is different to the extent that it is visible. Therefore, when importance is attached to the fastness, C.I. I. Acid red 138 but C.I. I. If the color tone of Acid Red 138 is not the desired color tone, C.I. I. Acid Violet 48 and C.I. I. By adding at least one selected from the group consisting of Acid Violet 97, it is possible to use the magenta ink in the desired color tone.

  Similarly, C.I. I. Although the acid blue 112 has a wide color reproduction range, it has the property that the fastness is somewhat low. On the other hand, C.I. I. Acid Blue 140 has a color reproduction area of C.I. I. Although slightly narrower than Acid Blue 112, it has the property of high robustness. And C.I. I. Acid Blue 112 and C.I. I. The color tone of Acid Blue 140 is different to the extent that it can be visually recognized. Therefore, when importance is attached to the fastness, C.I. I. Acid Blue 140 will be selected. I. If the color tone of Acid Blue 140 is not the desired tone, C.I. I. Acid Violet 48 and C.I. I. By adding at least one selected from the group consisting of Acid Violet 97, it is possible to use the blue ink to be adjusted to a desired color tone.

  In each color ink constituting the ink set according to the present embodiment, the zinc content of each color ink is preferably 50 ppm or less. When the zinc content of each color ink is 50 ppm or less, the storage stability of each color ink can be further improved. In particular, C.I. I. The acid black 172 is excellent in fastness (dyeability) to nylon and wool other than silk, and further to a mixture of silk and urethane, but the viscosity of the ink may increase with time. This is C.I. I. When the black ink contains a by-product produced when producing the acid black 172, the reaction between the by-product and the zinc ion may cause a phenomenon that the viscosity of the ink increases with time. . Therefore, by setting the zinc content in the black ink to 50 ppm or less, this phenomenon can be effectively suppressed, and the fastness to nylon and wool other than silk, and further to a blended fabric of silk and nylon and urethane ( Ink set which is excellent in dyeability).

  In each color ink constituting the ink set according to the present embodiment, a specific acid dye may be used as it is as a commercial product, but from the viewpoint of making the zinc content of each color ink 50 ppm or less, purification treatment It is preferable to apply The purification treatment may be performed on the acid dye itself, or may be performed after an ink containing the acid dye is prepared. The purification treatment is not particularly limited, and for example, known recrystallization methods, washing and the like can be used.

1.2. Moisturizing Agent It is preferable that the ink of each color constituting the ink set according to the present embodiment contain a moisturizing agent from the viewpoint of improving the ejection stability from the nozzle of the recording head of the ink jet printer. As the humectant, compounds used as a humectant in ordinary ink jet printing inks can be used, and examples thereof include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, and dipropylene. Glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, penta Polyols such as erythritol and derivatives thereof such as ethers or esters thereof; Lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam, etc .; urea, thiourea, ethylene urea, 1,3- Ureas such as methyl imidazolidinone; maltitol, sorbitol, gluconolactone, can be mentioned saccharides of maltose, it can be used alone or in combination. The content of the humectant is preferably 4 to 40% by mass with respect to the total mass of the ink composition.

1.3. Penetration Agent The ink of each color constituting the ink set according to the present embodiment contains a penetrant (a substance that imparts permeability to the ink) from the viewpoint of enhancing the wettability to the fabric to enhance the permeability of the ink. Is preferred. As such a permeable organic solvent, a compound used as a permeable organic solvent in a common ink jet printing ink can be used. For example, lower alcohols such as ethanol and propanol; ethylene glycol monomethyl ether, ethylene glycol Cellosolves such as monoethyl ether and ethylene glycol monobutyl ether; carbitols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; glycol ethers such as triethylene glycol monobutyl ether; One kind or two or more kinds can be used. The content of the permeable organic solvent (penetrating agent) is preferably 2 to 15% by mass with respect to the total mass of the ink composition.

  Furthermore, from the same viewpoint, in addition to the permeable organic solvent, a permeable surfactant may be further added to each color ink as a penetrant. As such a permeable surfactant, a compound used as a permeable surfactant in a general ink jet printing ink can be used. For example, an anionic surfactant such as a fatty acid salt; alkyl sulfate ester salt Nonionic surfactants such as polyoxyethylene alkylphenyl ether; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octin-3,6- Acetylene glycol surfactants such as diol, 3,5-dimethyl-1-hexyn-3-ol, 2,4-dimethyl-5-hexyn-3-ol; cationic surfactants; zwitterionic interface Activators; polyorganosiloxane surfactants and the like can be mentioned, and one or more of these can be added. The content of the surfactant (penetrant) which may be further added is preferably 0.2 to 2% by mass with respect to the total mass of the ink composition.

  In addition, it is possible to use a commercial item as the above-mentioned surfactant, and for example, as an acetylene glycol surfactant, Surfynol 61, 82, 104, 440, 465, 485 (all are trade names, Air Products · Air Products) And chemicals, etc. can be used.

1.4. Water In addition to the components described above, the ink of each color that constitutes the ink set according to the present embodiment contains water. As water, it is preferable to use pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water, or ultrapure water. In particular, water obtained by sterilizing such water by ultraviolet irradiation, hydrogen peroxide addition or the like is preferable because generation of mold and bacteria is prevented over a long period of time.

1.5. Other Additives In the ink of each color constituting the ink set according to the present embodiment, if necessary, a fungicide, preservative, antioxidant, ultraviolet absorber, chelating agent, oxygen absorber, pH adjustment An additive (for example, tertiary alkanolamine such as triethanolamine) or a solubilizing agent may contain one or more of various additives which can usually be used in the ink for ink jet printing.

1.6. Production and Properties of Each Color Ink The ink of each color constituting the ink set according to the present embodiment supplies each component described above to a dispersing / mixing machine (for example, a ball mill, sand mill, attritor, basket mill, roll mill, etc.) It can be prepared by dispersing. Moreover, it is preferable to filter the ink undiluted | stock solution obtained by above-described dispersion / mixer using filters, such as a membrane filter and a mesh filter, and to remove coarse particles.

  The surface tension of each color ink constituting the ink set according to the present embodiment is preferably 25 to 40 mN / m, and preferably 28 to 35 mN, from the viewpoint of the balance between printing quality and reliability as an ink for ink jet textile printing. It is more preferable that it is / m. From the same viewpoint, the viscosity at 20 ° C. of each color ink is preferably 1.5 to 10 mPa · s, and more preferably 2 to 8 mPa · s. In order to make surface tension and viscosity into the said range, the method of adjusting the density | concentration of the said acid dye, a means etc. which adjust the kind of the said moisturizer, addition amount, etc. can be used.

2. Ink jet textile printing method The ink jet textile printing method according to the embodiment comprises an ink jet printing process in which the ink is attached to one side of the fabric using the above-described ink set for ink jet textile printing, and a penetrant liquid on the fabric surface to which the ink is attached. And D. a cloth surface treatment step of adhering According to the inkjet printing method according to the present embodiment, an image having excellent fastness and light resistance can be formed on various fabrics. Further, by causing the penetrant to adhere to the fabric, after the ink soaks in the thickness direction of the fabric, it is possible to impart a penetrant effect to the fabric by the penetrant. Thereby, penetration in the lateral direction of the fabric is suppressed, and ink bleeding can be reduced.

2.1. Ink jet printing process The ink jet printing process is performed by adhering the ink of each color which comprises the above-mentioned ink set to the printing surface of a fabric by an inkjet system. Specifically, the ink cartridge of an ink jet printer is filled with each color ink, and ink droplets are ejected from the recording head to the fabric. As an ink jet printer, although a continuous system, a drop on demand system, etc. are applicable, a drop on demand type ink jet printer is preferable. The drop-on-demand type ink jet printer is generated by a piezo method (a method of performing recording using a piezoelectric element provided in a recording head), a thermal method (a heater of a heating resistance element provided in the recording head, etc.) There is a method of recording using air bubbles, etc., and any inkjet method can be adopted, but a piezo method is preferable.

  In the ink jet printing process, the evaporation rate of each color ink is susceptible to the amount of the penetrant attached to the fabric and the environment in which printing is performed. Also, each color ink is easy to evaporate because it contains water. Therefore, it is preferable that the ink jet printing process is carried out at 21 to 25 ° C. under an environment of 45 to 55% RH.

2.2. Fabric Surface Treatment Step Subsequently, a fabric surface treatment step is performed in which the penetrant liquid is attached to the printing surface to which the ink is attached. By causing the penetration liquid to adhere to the printing surface to which the ink has been attached after the ink has penetrated in the thickness direction of the fabric, it is possible to reduce the ink bleeding.

  The fabric surface treatment step is preferably performed before the ink attached to the fabric in the ink jet printing process completely evaporates from the fabric. Here, "completely evaporate" means that the liquid component that dissolves the acid dye in the ink does not remain on the fabric.

  In the present embodiment, the amount of the permeation liquid attached to the fabric is preferably 70 to 130% of the amount of ink applied to the fabric. By setting the adhesion amount of the penetrant solution within the above range, ink bleeding can be effectively reduced.

  In addition to the penetrant, the penetrant used in the present embodiment may contain water, a pH adjuster, and other additives.

  As the penetrant, a penetrable organic solvent and a penetrable surfactant which are usually used in the ink jet printing ink can be suitably used. As such a permeable organic solvent, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, trilyl. Polyhydric alcohols such as methylol ethane and trimethylol propane; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, triethylene glycol Monomethyl ether, to Many ethylene glycol monoethyl ether, triethylene glycol monobutyl ether, hexaethylene glycol monoethyl hexyl ether (manufactured by Nippon Emulsifier Co., Ltd .: Newcoal 1006), tetraethylene glycol monoethylhexyl ether (manufactured by Nippon Emulsifier Co., Ltd .: Newcoal 1004), etc. And alkyl ethers of polyhydric alcohols; urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Further, as alkyl ethers of polyhydric alcohols, triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, hexaethylene glycol monoethylhexyl ether, tetraethylene glycol mono Ethyl hexyl ether may be used alone or in combination of two or more. The permeation liquid preferably contains 10 to 30% by mass of the above-mentioned permeable organic solvent based on the total mass of the permeation liquid.

  Moreover, as a permeable surfactant, for example, fatty acid salts; anionic surfactants such as alkyl sulfate ester salts; nonionic surfactants such as polyoxyethylene alkylphenyl ether; Surfynol 61, 82, 104, 440 465, 485 (all are trade names, manufactured by Air Products & Chemicals Co., Ltd.), Orphine E1010, Orphine STG, Orphine Y (all trade names, manufactured by Nisshin Chemical Industry Co., Ltd.), etc. Agents; cationic surfactants; amphoteric surfactants; organopolysiloxane-based interfaces such as KF-353A, KF 6017, X-22-6551, AW-3 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) An activator etc. can be mentioned. The penetrant preferably contains 0.1 to 3% by mass of the above-mentioned osmotic surfactant.

  The permeation liquid used in the present embodiment may contain an organic amine as a pH adjuster in order to adjust the pH with each color ink. As the organic amine, tertiary amines are preferably used, and examples thereof include alkanolamines such as triethanolamine. The content of the organic amine is 0.05 to 3% by mass with respect to the total mass of the permeation liquid.

  The penetrant used in the present embodiment contains water in addition to the components described above. As water, it is preferable to use pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water, or ultrapure water. In particular, water obtained by sterilizing such water by ultraviolet irradiation, hydrogen peroxide addition or the like is preferable because generation of mold and bacteria is prevented over a long period of time.

  The penetrant liquid used in the present embodiment is generally used in ink jet printing inks, such as a mildewproofing agent, preservative, antioxidant, UV absorber, chelating agent, oxygen absorber, solubilizer, etc., as necessary. It can contain one or more of various additives that can be used.

  In the present embodiment, it is preferable to carry out the cloth surface treatment step also by the inkjet method. That is, as in the above-described inkjet printing process, it is preferable that the penetrant liquid be filled in the cartridge and the droplet of the penetrant liquid be ejected from the printer head to the printing surface to which the ink is attached. . In that case, it is preferable to set it as the inkjet system similar to an inkjet printing process, and implementation environment. By performing the cloth surface treatment step by the ink jet method, the penetrant can be discharged on demand onto the printing surface to which the ink of the cloth is attached, and the process is simplified and the productivity is improved. preferable.

2.3. Pretreatment process In the inkjet textile printing method concerning this embodiment, before performing the above-mentioned ink jet printing process and fabric surface treatment process, you may pre-treat a textile beforehand. For pretreatment of the fabric, known pretreatment agents can be used, and the pretreatment agents generally include a sizing agent, a pH adjuster, and a hydrotrope agent, and may further include silica.

  As the sizing agent, for example, natural gums such as guar gum and locust bean gum, starches, seaweeds such as sodium alginate and fusori, plant peels such as pectic acid, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose Fibrin derivatives such as roasted starch, processed starch such as roasted starch, alpha starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch etc., processed natural gum such as shiratsu gum type, roasted bean gum type, algin derivative or polyvinyl alcohol Synthetic glues such as polyacrylates, emulsions, etc. are used.

  Further, as a pH adjuster, an acid ammonium salt such as ammonium sulfate or ammonium tartrate is desirable. Furthermore, hydrotropes include alkylureas such as urea, dimethylurea, thiourea, monomethylthiourea, or dimethylthiourea.

2.4. Post-Treatment Step In the ink jet printing method according to the present embodiment, it is preferable to perform the dye fixing process after the above-described ink jet printing process is performed. In the dye fixing process, for example, a fixing operation can be performed using a known Steamer (manufactured by Matisse; Steamer DHe type). Specifically, steaming treatment is performed, for example, under high humidification conditions of a temperature of 102 ° C. for 30 minutes.

  Thereafter, the washing operation is performed. Specifically, after washing and washing the fabric with tap water, a nonionic soaping agent is added to warm water of about 50 ° C., and the fabric is dipped for about 15 minutes with occasional stirring. The bath ratio (printed cloth mass / bath mass) is preferably 1/50. Furthermore, wash it by hand while putting tap water in the cleaning solution. After sufficient washing with water, the cloth can be dried and ironed to obtain a printing cloth.

2.5. Printer Head As described above, the inkjet textile printing method in this embodiment can be applied to any inkjet system such as a thermal system, a continuous system, or a piezo system, but is preferably a piezo system.

Further, in the present embodiment, when the color ink and the penetrant liquid are filled in the printer head and discharged, it is preferable that the surface of the nozzle plate of the printer head is subjected to the ink repellent treatment. By applying the ink repellent treatment, it becomes difficult for the ink to fly and the desired image with excellent reproducibility can be printed on the fabric.

  Moreover, it is preferable to perform an ink repellent process also to the inner surface of a nozzle hole. By applying to the inner surface, the ink meniscus position is stabilized, and the ejection stability is further improved. In addition, the ink is less likely to come out on the surface of the nozzle plate, and the ink repellency of the surface of the nozzle can be maintained for a longer time.

  The nozzle plate can be provided with holes having a desired bore diameter. As a constituent material of the nozzle plate, metal, ceramics, silicon, glass, or plastic can be mentioned, and preferably, a single material such as titanium, chromium, iron, cobalt, nickel, copper, zinc, tin, or gold Or alloys of nickel-phosphorus alloy, tin-copper-phosphorus alloy, copper-zinc alloy, stainless steel, etc., polycarbonate, polysulfone, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polysulfone, or various photosensitivity It is desirable to form with resin.

  Although the method of ink repellent treatment of the surface of these materials is not particularly limited, for example, it is immersed in an electrolytic solution in which nickel ions and water repellent polymer resin particles are dispersed by electric charge, and immersed while stirring the electrolytic solution The preferred method is eutectoid plating on the surface of the nozzle plate. As a water-repellent polymer resin material used for this eutectoid plating, resins such as polytetrafluoroethylene, polyperfluoroalkoxy butadiene, polyfluorovinylidene, polyfluorovinyl, or polydiperfluoroalkyl fumarate, alone or mixed Is preferably used. The metal material is not limited to nickel, and, for example, copper, silver, tin, zinc or the like can be appropriately selected. Preferably, materials having high surface hardness and excellent abrasion resistance, such as nickel, nickel-cobalt alloy, or nickel-boron alloy, are suitable.

2.6. Fabric As a fabric suitably used in the ink jet textile printing method by this embodiment, a fabric (for example, textiles, nets, or a nonwoven fabric) which consists of polyamide system fiber and / or cellulose system fiber is mentioned. Examples of cellulose fibers include cotton, hemp, rayon, polynozic, cupra, lyocell and the like. Examples of polyamide fibers include silk, wool and nylon. According to the ink jet printing method according to the present embodiment, since the above-described ink set is used, an image excellent in fastness and light resistance to not only silk but also nylon or wool, and a blend of silk or nylon and urethane is formed. be able to.

3. EXAMPLES Hereinafter, the embodiments of the present invention will be more specifically described by examples and comparative examples, but the present invention is not limited by these examples.

3.1. Preparation of Permeate According to the composition shown in Table 1 below, each component was mixed to prepare a permeate. In Table 1, TEG-m-BE represents triethylene glycol monobutyl ether, and Proxel X
L2 represents a mildew proofing agent (preservative) manufactured by Lonza Japan Co., Ltd. The numerical values in Table 1 represent% by mass.

3.2. Preparation of ink set (each color ink) Each component was mixed according to following Table 2-Table 5, six color ink of each color was prepared, and this was made into the ink set. In Table 2, TEG-m-BE and Proxel XL2 represent the same as those in Table 1, and EDTA represents disodium ethylenediaminetetraacetate. The numerical values in Tables 2 to 5 represent% by mass.

  In Table 4, “Acid Orange 33” used was purified as follows. That is, 7.0 g of unrefined Acid Orange 33 dye (manufactured by Haihang Industry Co., Ltd.) was dissolved in 100 g of water, 50 g of activated carbon (particulate) was added to it, and stirred for 1 day. After removing the activated carbon by filtration, a dye solid was obtained by an evaporator and drying under reduced pressure.

3.3. Ink jet printing and evaluation method <Gamat volume>
Each ink set of Examples and Comparative Examples was printed on the surface (surface to be printed) of the fabric at a resolution of 1440 × 720 dpi using an inkjet printer (PX-G 930, manufactured by Seiko Epson Corporation). At this time, the duty of 100% single color and 13 mg / inch ^2, the Duty of the mixed color 120%, and a 16 mg / inch ^2. The duty of each of these is the highest duty, the duty of each single-color ink is in the range of 0% to 100%, the duty is changed by 3%, and a total combination of each ink is performed in each ink set. All reproducible colors were printed to obtain each recorded matter. In addition, three types of silk, wool, and a blend of nylon and urethane were used as the fabric.

Each color of each recorded material is viewed at a viewing angle of 2 using Gretag Macbeth SPM 50 manufactured by Gretag Co.
Measured with a D50 illuminant, and defined by CIE, to obtain L ^* a ^* b ^* .

From the values obtained in this manner, the gamut volume (= color reproducibility) was determined, assuming that the gamut volume is 1 when all the L ^* a ^* b ^* values specified in CIE are 1. From this value, it was determined as follows.
A: The gamut volume is 35,000 or more.
B: The gamut volume is 25,000 or more and less than 35,000.
C: The gamut volume is at least 20,000 and less than 25,000.
D: The gamut volume is less than 20,000.

<Washing fastness>
The six ink sets described above as the ink jet printing process are respectively filled in the six heads of an ink jet printer (PX-G 930, Seiko Epson Corporation) having eight rows (for eight colors) of nozzle rows, and the remaining two Set the penetrant in one of the rows and print solid ink (100% duty of color ink and 100% duty of penetrant (total 200% duty) at a resolution of 1440 x 720 dpi on the surface (printed side) of the fabric The applied amount of one ink was 20 mg / inch ² ) per unit area of the fabric. Thus, a solid printed printed material was prepared for each color. In addition, three types of silk, wool, and a blend of nylon and urethane were used as the fabric. Subsequently, the printed material obtained by steaming treatment for 30 minutes under highly humidified conditions of 102 ° C. using a steamer (made by Matisse; steamer DHe type) was washed by a method according to ISO 105-C10: 2006 Robustness evaluation was performed. Evaluation criteria are as follows.
A: About the wash fastness of the ink set, the result of the color with the lowest level is 4 or higher. B: About the washing fastness of an ink set, the result of the color with the lowest level is 3rd grade or more and less than 4th grade.
C: About the washing fastness of an ink set, the result of the color with the lowest level is 2 grade or more and less than 3 grade.
D: Regarding the washing fastness of the ink set, the result of the lowest color is less than second grade.

<Sweat fastness>
The six ink sets described above as the ink jet printing process are respectively filled in the six heads of an ink jet printer (PX-G 930, Seiko Epson Corporation) having eight rows (for eight colors) of nozzle rows, and the remaining two Set the penetrant in one of the rows and print solid ink (100% duty of color ink and 100% duty of penetrant (total 200% duty) at a resolution of 1440 x 720 dpi on the surface (printed side) of the fabric The applied amount of one ink was 20 mg / inch ² ) per unit area of the fabric. Thus, a solid printed printed material was prepared for each color. In addition, three types of silk, wool, and a blend of nylon and urethane were used as the fabric. Subsequently, the printed material obtained by steaming treatment for 30 minutes under highly humidified conditions of 102 ° C. using a steamer (made by Matisse; steamer DHe type) is sweated by a method according to ISO 105-E04: 1994 Robustness (acid sweat resistance, alkaline sweat resistance) was evaluated. Evaluation criteria are as follows.
A: About the sweat fastness of the ink set, the result of the color with the lowest level is grade 4 or higher.
B: About the sweat fastness of an ink set, the result of the color with the lowest level is 3 grade or more and less than 4 grade.
C: About the sweat fastness of an ink set, the result of the color with the lowest level is 2 grade or more and less than 3 grade.
D: The result of the color with the lowest level is less than second in the sweat fastness of the ink set.

<Light resistance>
The six ink sets described above as the ink jet printing process are respectively filled in the six heads of an ink jet printer (PX-G 930, Seiko Epson Corporation) having eight rows (for eight colors) of nozzle rows, and the remaining two Set the penetrant in one of the rows and print solid ink (100% duty of color ink and 100% duty of penetrant (total 200% duty) at a resolution of 1440 x 720 dpi on the surface (printed side) of the fabric The applied amount of one ink was 20 mg / inch ² ) per unit area of the fabric. Thus, a solid printed printed material was prepared for each color. In addition, three types of silk, wool, and a blend of nylon and urethane were used as the fabric. Next, steaming treatment is carried out using a steamer (Matisse Co., Ltd .; Steamer DHe type) under highly humidified conditions of 102 ° C. for 30 minutes, and then Laccoll STA (manufactured by Meisei Chemical Co., Ltd., surfactant) is 0.2. The resulting printed matter was subjected to light resistance evaluation according to ISO 105-B02: 1994, using a Xenon light resistance tester, after washing with an aqueous solution containing 10% by mass for 10 minutes at 55 ° C. and drying. . The evaluation criteria of light resistance are as follows. A: Regarding the light fastness of the ink set, the result of the color with the lowest level is grade 5 or higher.
B: With respect to the light resistance of the ink set, the result of the color with the lowest level is 4 or more and less than 5 or less.
C: With respect to the light resistance of the ink set, the result of the color with the lowest level is grade 3 or more and less than grade 4.
D: Regarding the light resistance of the ink set, the result of the lowest color is less than grade 3.

<Storage stability>
By mixing and stirring each component described in Table 6, black inks 1 to 3 for ink jet printing were prepared. In Table 6, PD002W represents Olfin PD002W (acetylene glycol surfactant manufactured by Nisshin Chemical Industry Co., Ltd.). Each black ink was filled in the head of an ink jet printer (PX-G 930, manufactured by Seiko Epson Corporation). After filling, print the nozzle check pattern and check that there are no filling defects and nozzle clogging, then turn off the printer and put the head back to the home position, temperature 40 ° C, humidity It was left for 2 weeks in an environment of 10 to 20% RH. After standing, a cleaning operation was performed as necessary, and 30 nozzle check patterns were continuously printed. The storage stability of the ink was evaluated by observing the number of missing nozzles at this time. The evaluation criteria are shown below.
A: No nozzle missing when 30 sheets are continuously discharged.
B: 1 or more and less than 5 nozzles missing when continuously discharging 30 sheets.
C: 5 or more missing nozzles when continuously discharging 30 sheets.

3.4. Evaluation Results The compositions of the inks used in the ink sets of the Examples and Comparative Examples and the results of the evaluation tests are shown in Tables 2 to 6.

  From the results of Tables 3 to 5, it was found that a wide color reproduction area can be secured also in the ink sets of Examples 1 to 3. Further, solid orange images in the ink sets of Examples 1 to 3 are superior to solid orange images in the ink set of Comparative Example 1 in terms of washing fastness, sweat fastness and light resistance, and as a whole, The ink sets of Examples 1 to 3 were also superior in washing fastness, sweat fastness and light fastness.

  Also, from the results of Table 6, C.I. I. In the black ink containing the acid black 172, it was found that when the amount of zinc contained in the ink exceeds 50 ppm, the viscosity increases with time and the number of occurrences of nozzle missing increases.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the invention includes configurations substantially the same as the configurations described in the embodiments (for example, configurations having the same function, method and result, or configurations having the same purpose and effect). The present invention also includes configurations in which nonessential parts of the configurations described in the embodiments are replaced. The present invention also includes configurations that can achieve the same effects as the configurations described in the embodiments, or configurations that can achieve the same purpose. Further, the present invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (5)

As a colorant, C.I. I. Yellow ink containing Acid Yellow 79,
As a colorant, C.I. I. Acid Red 138 and C.I. I. Magenta ink containing at least one selected from the group consisting of Acid Red 289;
As a colorant, C.I. I. Cyan ink containing Direct Blue 87,
As a colorant, C.I. I. Acid Orange 33 and C.I. I. An orange ink containing at least one selected from the group consisting of Acid Orange 94;
As a colorant, C.I. I. Acid Blue 112 and C.I. I. Blue ink containing at least one selected from the group consisting of Acid Blue 140;
As a colorant, C.I. I. Black ink containing acid black 172,
An ink set for ink jet printing comprising:   The ink set for ink jet textile printing according to claim 1, wherein each of the inks contains 50% by mass or more of an acid dye contained as the colorant when the total amount of the colorant is 100% by mass.   In at least one of the respective inks, C.I. I. Acid Violet 48 and C.I. I. The ink set for ink jet printing according to claim 1 or 2, further comprising at least one selected from the group consisting of Acid Violet 97.   The ink set for ink jet textile printing according to any one of claims 1 to 3, wherein the zinc content of each of the inks is 50 ppm or less. The inkjet printing process which makes an ink adhere to one side of a fabric using the ink set for inkjet textiles as described in any one of Claims 1-4.
A cloth surface treatment step of causing a penetrant to adhere to the cloth surface simultaneously with the ink;
An ink jet printing method comprising: