JP2011174207A - Ink jet printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet printing method which can perform pretreatment of cloth without conventional coating or padding methods and can attain high dye concentration. <P>SOLUTION: With the ink jet printing method, the ink containing acid dye is printed to a cloth by the ink jet method. It includes a preparation process in which liquid composition containing polyhydric alcohol whose hydroxyl value is 890-1,070 is made to adhere to the cloth and an ink jet printing process in which the ink composition containing acid dye is discharged to the pretreated cloth while the liquid composition adhering to the cloth remains in the cloth. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an inkjet printing method, and more particularly to a method of performing inkjet printing with an acid dye ink after pre-treating a fabric using a specific liquid composition.

  Conventionally, a screen printing method, a roller printing method, a rotary screen printing method, a transfer printing method, or the like is used as a method for printing an image on a fabric. However, it is necessary to prepare expensive screen frames, engraving rollers, transfer paper, etc. for every change in image design, so it is not suitable for low-volume production of various products and responds quickly to diversification of fashion. It was difficult.

  In order to eliminate the disadvantages of the conventional printing method, a technique 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 ink jet method. The ink jet 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 attached to the recording medium. The mechanism is relatively simple and inexpensive. In addition, a high-definition and high-quality image can be formed. When such an ink jet method is applied to a printing method, it is not necessary to prepare a plate that is required in the conventional printing method, and an image having excellent gradation can be quickly formed. There is an advantage that it is possible to deal with small-quantity production. Further, according to the ink jet system, since only a necessary amount of ink is used at the time of image formation, there is an environmental advantage such as less waste liquid as compared with conventional screen printing or the like.

  However, when the ink jet method is directly applied to textile printing or the like, there is a problem that bleeding is remarkable and sharpness is inferior. That is, unlike paper, fabric has directionality in the fiber structure and woven structure, and the gap is larger than that of paper. Therefore, when the ink ejected from the ink head adheres to the fabric, the fabric bleeds in the vertical and horizontal directions and becomes clear. Can not get a good image. In addition, as described above, since the ink jet method ejects ink droplets from the ink head, it is not possible to directly apply a high viscosity ink like a conventional textile printing ink, and a low viscosity ink is used. This causes more bleeding and makes it difficult to increase the dyeing density of the fabric.

  For the above problem, before the ink is attached to the cloth, only the high viscosity component in the dye ink is attached to the cloth in advance by coating or padding method, and the pretreated cloth has a low viscosity. There has been proposed a method for performing textile printing by an ink jet method using the above dye ink (for example, Japanese Patent Publication No. 63-31594: Patent Document 1). However, in the textile printing method in which the pre-treatment as described above is performed, the pre-treatment agent is fixed after the pre-treatment and the ink-jet textile printing is performed after the fabric is washed.

  In response to such a problem, for example, in Japanese Patent Publication No. 2007-102455 (Patent Document 2), when inkjet printing is performed using a disperse dye, polyglycerin and alkanediol or polypropylene glycol are contained in a predetermined ratio in the ink. It is proposed that a fabric with less bleeding and excellent fastness can be obtained without adding a pretreatment.

Japanese Examined Patent Publication No. 63-31594 Special table 2007-102455 gazette

  The present inventors have intensively studied a pretreatment agent that can be ejected from an ink head of an ink jet recording apparatus and attached to a cloth without using a coating or padding method as in the past. It has been found that the ink jet method can be applied to any liquid composition containing a polyhydric alcohol having a specific hydroxyl value. And after making this liquid composition adhere to a cloth beforehand, while the liquid composition remains on the cloth, the ink containing an acid dye is ejected to the part to which the liquid composition has been attached by an inkjet method. It has been found that the dyeing density is drastically improved by printing. The present invention is based on such knowledge.

  Accordingly, an object of the present invention is to provide an ink-jet printing method capable of pre-treating a fabric without using a coating or padding method as in the prior art and realizing a high dyeing density.

The inkjet printing method according to the present invention is an inkjet printing method in which an ink containing an acid dye is printed on a fabric by an inkjet method,
A pretreatment step of attaching a liquid composition comprising a polyhydric alcohol having a hydroxyl value of 890 to 1070 to the fabric;
An ink jet printing step of discharging an ink composition containing an acid dye to the pretreated fabric while the liquid composition adhering to the fabric remains on the fabric;
Is included.

  According to the ink-jet textile printing method of the present invention, it is possible to perform pre-treatment of a fabric by an ink-jet method and achieve a high dyeing density without using a coating or padding method as in the prior art.

Detailed description of the invention

  In the inkjet printing method according to the present invention, 1) a pretreatment step of attaching a liquid composition comprising a polyhydric alcohol having a hydroxyl value of 890 to 1070 to a cloth; and 2) a liquid composition attached to the cloth. An ink jet printing process in which an ink composition containing an acid dye is ejected onto the pretreated fabric while remaining on the fabric. Hereinafter, each step will be described in detail.

<Pretreatment process>
Conventionally, it is known that a fabric is pretreated before printing on the fabric using an acid dye. In the ink jet textile printing method according to the present invention, a liquid composition comprising a polyhydric alcohol having a hydroxyl value of 890 to 1070 is used as the treatment liquid used in the pretreatment step of the fabric. The fabric is pretreated with a liquid composition containing a polyhydric alcohol having a hydroxyl value within the above range, and the inkjet printing process described later is performed while the liquid composition adhering to the fabric remains on the fabric. To do. As described above, the ink-jet printing process is performed while the cloth is pretreated with the liquid composition containing the polyhydric alcohol having a hydroxyl value within the above range and the liquid composition remains on the cloth. By carrying out the above, it is possible to obtain a fabric with less bleeding and a high dyeing density. In addition, a liquid composition containing a polyhydric alcohol having a hydroxyl value within the above range has a significantly lower viscosity than a conventional pretreatment agent used for pretreatment of a fabric, and therefore, an inkjet method is applied. The liquid composition can be adhered to the fabric. As a result, for example, the liquid composition and the dye ink composition can be filled in the same cartridge, and the liquid composition and the dye ink can be discharged from individual printer heads. Can be implemented using a single inkjet printer. Therefore, a series of ink-jet printing processes can be greatly simplified as compared with the case where the treatment liquid (liquid composition) is attached to the fabric by a coating or padding method as in the past.

  The liquid composition used for the pretreatment of the fabric includes a polyhydric alcohol having a hydroxyl value of 890 to 1070. If the hydroxyl value is less than 890 or exceeds 1070, the dyeing concentration may not be high and bleeding may be a problem. In the present specification, the “hydroxyl value” means a value measured according to JIS K 0070 (1992). That is, it is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample (polyhydric alcohol) is acetylated. Specifically, precisely weighed sample Xg (about 1 g) was put into a flask equipped with an air cooling tube, and 20 ml of an acetylating reagent (20 ml of acetic anhydride added to 400 ml) was accurately added. The flask is heated in a glycerin bath at 95-100 ° C. for 1 hour 30 minutes, then cooled, 1 ml of purified water is added from an air cooling tube, acetic anhydride is decomposed into acetic acid, and then a potentiometric titrator is used. Titration with 0.5 mol / L potassium hydroxide ethanol solution, with the inflection point of the obtained titration curve as the end point, and as a blank test, from the inflection point of the titration curve when titrating without adding a sample, Calculate the hydroxyl value.

（式中、ｎは４〜１０の整数を表す。） The polyhydric alcohol contained in the liquid composition is preferably polyglycerin represented by the following formula (1).

(In the formula, n represents an integer of 4 to 10.)

  For example, polyglycerin # 310 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) is exemplified as the polyglycerin having n of 4 in the above formula (1), and the hydroxyl value thereof is 1070. Moreover, polyglycerin # 750 (made by Sakamoto Pharmaceutical Co., Ltd.) is mentioned as a polyglycerin whose n of the said Formula (1) is 10, The hydroxyl value is 890. Polyglycerin in which n in the above formula (1) is 3 or less has a hydroxyl value exceeding 1070, so that the dyeing concentration does not increase and bleeding may not be improved. In addition, since the polyglycerin in which n in the above formula (1) is 11 or more has a hydroxyl value of less than 890, the dyeing concentration does not increase and bleeding may not be improved.

  The polyhydric alcohol described above is preferably contained in an amount of 10 to 30% on a mass basis with respect to the liquid composition. If the polyglycerin content is less than 10%, the dyeing concentration may not be high, and bleeding may not be improved. On the other hand, if the content of polyglycerin exceeds 30%, the de-glue property may be lowered during washing after dyeing, and the texture of the fabric may be deteriorated.

  The liquid composition used in the present invention contains various additives such as a moisturizer such as urea or thiourea, a pH adjuster, a reduction inhibitor, a penetrant, a sequestering agent, or an antifoaming agent, as necessary. Can also be included.

<Inkjet printing process>
In the present invention, as described above, after pre-treating a fabric, an ink composition containing an acid dye is ejected onto the fabric for printing. The ink jet printing needs to be performed while the liquid composition adhering to the cloth remains on the cloth in the pretreatment step. It is surprising that by performing inkjet printing in a state where the polyhydric alcohol component in the liquid composition remains in the liquid state, not only bleeding but also the dyeing density of the fabric is remarkably improved. Met. “The liquid composition remains on the fabric” means that the polyhydric alcohol component of the liquid composition remains on the fabric in a liquid state, and the evaporation of the liquid composition is in an equilibrium state. And the case of non-equilibrium state.

  After the liquid composition is adhered to the fabric, ink jet printing is performed while the liquid composition remains on the fabric. Specifically, within 16 hours after the liquid composition is adhered to the fabric. Ink jet printing is preferably performed within 4 hours. The remaining amount of the liquid composition adhering to the fabric usually decreases with the elapse of time due to evaporation of the liquid composition, but it is also affected by the amount of adhering the liquid composition to the fabric and the printing environment. To receive. In the present invention, the adhesion amount of the liquid composition to the fabric is preferably about 70 to 130% of the application amount of the ink composition to the fabric. By setting the adhesion amount of the liquid composition within the above range, a higher dyeing concentration can be realized. Moreover, it is preferable that the said pre-processing process and an inkjet textile printing process are implemented in an environment of 45-55% RH at 21-25 degreeC.

  The ink composition used in the ink jet printing process will be described. In the present invention, an ink composition containing an acid dye is used. When printing is performed using an ink containing an acid dye, bleeding and dyeing density are remarkably improved by applying the pretreatment process as described above. The acid dye can be used without particular limitation. For example, as the acid dye, C.I. I. Acid Yellow 1, 3, 7, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 70, 72, 75, 76, 78, 79, 98, 99, 110, 111, 112, 114, 116, 118, 119, 127, 128, 131, 135, 141, 142, 161, 162, 163, 164, 165, 169, 207, 219, 246, C.I. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 19, 24, 26, 27, 28, 32, 35, 37, 42, 51, 52, 57, 62, 75, 77, 80, 82, 83, 85, 87, 88, 89, 92, 94, 95, 97, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 149, 154, 155, 158, 168, 180, 183, 184, 186, 194, 198, 199, 209, 211, 215, 216, 217, 219, 249, 252, 254, 256, 257, 260, 262, 265, 266, 274, 276, 282, 283, 289, 303, 317, 318, 320, 321, 322, 361, C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 49, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 87, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 133, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 185, 187, 192, 199, 203, 204, 205, 225, 229, 234, 236, 300, C.I. I. Acid Black 1, 2, 7, 24, 26, 29, 31, 44, 48, 50, 51, 52, 58, 60, 62, 63, 64, 67, 72, 76, 77, 94, 107, 108, 109, 110, 112, 115, 118, 119, 121, 122, 131, 132, 139, 140, 155, 156, 157, 158, 159, 191, 234, C.I. I. Acid Orange 1, 7, 8, 10, 19, 20, 24, 28, 33, 41, 43, 45, 51, 56, 63, 64, 65, 67, 74, 80, 82, 85, 86, 87, 88, 95, 122, 123, 124, C.I. I. Acid Violet 7, 11, 15, 31, 34, 35, 41, 43, 47, 48, 49, 51, 54, 66, 68, 75, 78, 97, 106, C.I. I. Acid Green 3, 7, 9, 12, 16, 19, 20, 25, 27, 28, 35, 36, 40, 41, 43, 44, 48, 56, 57, 60, 61, 65, 73, 75, 76, 78, 79, C.I. I. Acid Brown 2, 4, 13, 14, 19, 20, 27, 28, 30, 31, 39, 44, 45, 46, 48, 53, 100, 101, 103, 104, 106, 160, 161, 165, 188, 224, 225, 226, 231, 232, 236, 247, 256, 257, 266, 268, 276, 277, 282, 289, 294, 295, 296, 297, 299, 300, 301, 302, etc. It is done.

  In the present invention, the content of the dye is not particularly limited, but is preferably 1 to 10% by mass, more preferably 2 to 7% by mass, based on the total weight of the ink composition. By setting the total content of the acid dyes to 1% by mass or more, a sufficient printing density can be obtained, and by setting the content to 10% by mass or less, the ejection stability required for the ink composition for inkjet is ensured. In particular, it is possible to prevent discharge failure particularly at high temperatures.

  The dye ink composition preferably contains a humectant from the viewpoint of improving the ejection stability from the nozzles of the recording head of the ink jet printer. As the humectant, a compound used as a humectant in a normal ink-jet printing ink composition can be used. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol , Dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexane Polyols such as triol or pentaerythritol, and derivatives thereof such as ethers or esters thereof; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, or ε-caprolactam; urea, thiourea, ester Examples include ureas such as renurea or 1,3-dimethylimidazolidinone; saccharides such as maltitol, sorbitol, gluconolactone, or maltose, and one or more of these may be used. it can. The content of the humectant is preferably 4 to 40% by weight with respect to the total weight of the ink composition.

  In addition, the dye ink composition preferably contains a water-soluble organic solvent that also functions as a penetrant from the viewpoint of increasing the wettability to the fabric and increasing the permeability of the ink. As such a penetrant organic solvent, a compound used as a penetrant organic solvent in a normal ink-jet printing ink composition can be used. For example, lower alcohols such as ethanol or propanol; ethylene glycol monomethyl ether Or cellosolves such as ethylene glycol monoethyl ether; carbitols such as diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; glycols such as ethylene glycol mono-n-butyl ether, diethylene glycol-n-butyl ether, or triethylene glycol-n-butyl ether Ethers etc. can be mentioned, These 1 type (s) or 2 or more types can be used. The content of the water-soluble organic solvent (penetrating agent) is preferably 2 to 15% by weight with respect to the total weight of the ink composition.

  Furthermore, from the same viewpoint, in addition to the water-soluble organic solvent, a surfactant that also functions as a penetrating agent may be added to the dye ink composition. As such penetrant surfactant, a compound that is used as a penetrant surfactant in a normal ink-jet printing ink composition can be used, and examples thereof include anionic properties such as fatty acid salts; alkyl sulfate ester salts and the like. Surfactant; Nonionic surfactant such as polyoxyethylene alkylphenyl ether; Acetylene such as Surfynol 61, 82, 104, 440, 465, 485 (all trade names, manufactured by Air Products and Chemicals) Examples thereof include glycol surfactants; cationic surfactants; amphoteric surfactants, and the like, and one or more of these can be added. The content of the surfactant (penetrating agent) that may be further added is preferably 0.2 to 2% by weight based on the total weight of the ink composition.

  In the present invention, as described above, the dye ink composition contains a dye, and if necessary, contains a moisturizing agent and a penetrating agent, and further contains water as a balance. As water, it is preferable to use ion-exchanged water, ultrafiltered water, reverse osmosis water, pure water such as distilled water, or ultrapure water. In particular, water obtained by sterilizing these waters by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bacteria is prevented for a long period of time.

  In the present invention, the dye ink composition may further include an antifungal agent, an antiseptic agent, an antioxidant, an ultraviolet absorber, a chelating agent, an oxygen absorber, a pH adjuster (for example, triethanolamine), if necessary. Alternatively, one or more of various additives that can be usually used in an ink composition for ink jet textile printing, such as a solubilizing agent, can be contained.

  The dye ink composition used in the present invention may be prepared by supplying the above-described components to a dispersing / mixing machine (for example, a ball mill, a sand mill, an attritor, a basket mill, a roll mill, etc.) and dispersing them. According to a preferred embodiment of the present invention, it is preferable to filter the ink stock solution obtained by the above-described dispersing / mixing device using a filter such as a membrane filter or a mesh filter to remove coarse particles.

  Such a dye ink composition preferably has a surface tension of 25 to 40 mN / m, preferably 28 to 35 mN / m, from the viewpoint of the balance between the printing quality and the reliability as an ink composition for ink jet textile printing. More preferably. From the same viewpoint, the viscosity of the ink composition according to the present invention at 20 ° C. is preferably 1.5 to 10 mPa · s, and more preferably 2 to 8 mPa · s. In order to make the surface tension and viscosity within the above ranges, a method for adjusting the concentration of the dye, a means for adjusting the type and amount of the humectant, and the like can be used.

  Examples of the cloth suitably used in the inkjet printing method according to the present invention include a cloth made of polyamide fiber, silk or wool (for example, a woven fabric, a net, or a non-woven fabric).

  Ink jet printing is performed by filling an ink cartridge of an ink jet printer with an ink composition and ejecting ink droplets from a printer head onto a fabric. The inkjet printer is not particularly limited, but a drop-on-demand inkjet printer is preferable. The drop-on-demand ink jet printer employs a piezoelectric element recording method in which recording is performed using a piezoelectric element disposed on a recording head, and heat energy generated by a heater of a heating resistance element disposed on the recording head. There is a method that employs a thermal jet recording method that performs recording using a recording medium, and any recording method can be employed.

  In the present invention, after ink jet printing, a dye fixing process is performed. Examples of the dye fixing treatment method include the same methods as the dye fixing treatment method in the conventional textile printing method, for example, a normal pressure steam method, a high pressure steam method, or a thermofix method. After the dye fixing treatment, the fabric is washed with water and dried as usual. If necessary, a soaping process (a process in which unfixed dye is washed away with a hot soap solution) may be performed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

<Preparation of fabric>
What applied each of the following 3 types of compositions 1-3 to a commercially available silk fabric (12cm) was squeezed with a mangle at a pick-up rate of 50% and dried at room temperature for 24 hours. Obtained.

Composition 1
Sodium alginate 4 parts by weight Gua gum 4 parts by weight Ammonium sulfate 4 parts by weight Ultrapure water 88 parts by weight (total) 100 parts by weight
Composition 2
Polyglycerin (where n in formula 1 is 2) 4 parts by weight Ammonium sulfate 4 parts by weight Ultrapure water 88 parts by weight (total) 96 parts by weight
Composition 3
Polyglycerin (where n in formula 1 is 12) 4 parts by weight Ammonium sulfate 4 parts by weight Ultrapure water 88 parts by weight (total) 96 parts by weight

<Preparation of liquid composition>
Each component was mixed according to the following Table 1, and the liquid compositions 1-8 were prepared. In Table 1, polyglycerin (n = 4) means polyglycerin in which n in the above formula (1) is 4, and polyglycerin (n = 10) means the above formula (1). N in the middle means 10 polyglycerol.

<Preparation of textile printing ink composition>
Next, each component was mixed according to the following Table 2, and the textile printing ink compositions 1-9 were prepared. In Table 2, polyglycerin (n = 4) means polyglycerin where n in the above formula (1) is 4, and polyglycerin (n = 10) means the above formula (1). N in the middle means 10 polyglycerol.

<Inkjet printing>
Each of the fabrics 1 to 3 obtained above was coated with the liquid compositions 1 to 8 obtained by the inkjet method using a PM-A750 printer (manufactured by Seiko Epson Corporation), and the fabric was opened in an open state. After being stored for a predetermined time according to the following Table 3 in an environment of ° C. and humidity of 55% RH, inkjet printing was performed using the dye ink compositions 1 to 9 at the place where the liquid composition of the fabric was applied.
Next, after the printed fabric was steamed and fixed at 100 ° C. for 30 minutes, Olfin E1010 (manufactured by Nissin Chemical Co., Ltd.), Lucal STA (manufactured by Meisei Chemical Co., Ltd.) 0.2% aqueous solution, A dyed concentration test piece was washed at 55 ° C. for 10 minutes and dried.
Using the obtained test piece, the optical density Db value was measured using Spectrolino (manufactured by Gretag Macbeth). The measurement results were scored according to the following score table. The PG liquid was also printed in the same manner, and printed on the cloth prior to the printing ink. After the application, the cloth was stored in an open state at 25 ° C. and a humidity of 55% RH for a specified time, and finished by printing with a printing ink.

Db value is 1.60 or more and less than 1.65: 6 points Db value is 1.55 or more and less than 1.60: 5 points Db value is 1.50 or more and less than 1.55: 4 points Db value is 1. 45 or more and less than 1.50: 3 points Db value is 1.40 or more and less than 1.55: 2 points Db value is less than 1.40: 1 point The evaluation results are as shown in Table 3 below. .

Claims (9)

An ink jet printing method for printing an ink containing an acid dye on a fabric by an ink jet method,
A pretreatment step of attaching a liquid composition comprising a polyhydric alcohol having a hydroxyl value of 890 to 1070 to the fabric;
An ink jet printing step of discharging an ink composition containing an acid dye to the pretreated fabric while the liquid composition adhering to the fabric remains on the fabric;
An ink-jet textile printing method comprising: The polyhydric alcohol is represented by the following formula (1):

(In the formula, n represents an integer of 4 to 10.)
The method of Claim 1 which is polyglycerin represented by these.   The method according to claim 1 or 2, wherein the polyhydric alcohol is contained in an amount of 10 to 30% on a mass basis with respect to the liquid composition.   The method according to any one of claims 1 to 3, wherein the inkjet printing step is performed within 16 hours after the pretreatment step.   5. The method according to claim 1, wherein in the pretreatment step, the amount of the liquid composition applied to the fabric is 70 to 130% by mass of the amount of the ink composition applied to the fabric.   The method according to any one of claims 1 to 5, wherein the pretreatment step and the inkjet printing step are performed in an environment of 45 to 55% RH at 21 to 25 ° C.   The method as described in any one of Claims 1-6 with which the said pre-processing process is implemented by the inkjet system which discharges the said liquid composition with respect to a fabric.   The method according to claim 7, wherein the liquid composition and the ink composition are filled in the same ink cartridge, and the pretreatment step and the printing step are performed by an inkjet method.   The method according to any one of claims 1 to 8, wherein the fabric is made of silk, wool, or polyamide-based fibers.