JP2012144637A - Ink set for printing and inkjet printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set for printing which can obtain uniform dyeability even by steam treatment in a short time and can obtain an image quality in which the bleeding of coloring is suppressed, and further, to provide an ink set for printing which suppresses bleeding even to a cloth not subjected to pretreatment and can obtain a high coloring density free from white spots by steam treatment in a short time, and an inkjet printing method.SOLUTION: The ink set for printing is composed of: an ink composition A at least comprising a copper phthalocyanine dye, a water-soluble organic solvent and ethylene urea; and an ink composition B comprising a dye other than a copper phthalocyanine dye, a water-soluble organic solvent and ethylene urea of <0.5 times (including zero time) of the content of the ethylene urea in the ink composition A.

Description

  The present invention relates to a novel ink set for textile printing and an ink jet textile printing method using the same. The present invention relates to an ink set for textile printing that can obtain a good image even on a fabric that is not, and an ink jet textile printing method using the same.

  In recent years, in the textile printing field, an inkjet textile printing method that does not require a plate making process has been applied as a means of shortening the delivery time and producing a small variety of products. In the ink-jet printing method, a printing material is applied onto a cloth using an ink-jet head and printed, and then a color treatment, mainly a dye, is fixed to the cloth by performing a steam treatment as a coloring process. In this treatment, there is a problem that the conditions for obtaining sufficient color developability and uniform dyeability and the necessary steam treatment time are different, so that the dye fixing speed between the dyes is made closer and the treatment time is further shortened. It is hoped that. As a result of the study by the present inventors, it has been found that, particularly when a copper phthalocyanine dye is used, there is a problem that colored spots occur when the steam treatment time is short.

  Moreover, in order to ensure the stable light emission of an inkjet ink, the method of adding cyclic urea, such as urea and ethylene urea, as a dye dissolution aid in an inkjet ink is known (for example, refer patent document 1).

  On the other hand, when an image is formed by directly ejecting conventional water-based ink for inkjet onto an untreated fabric, bleeding occurs. For this reason, a pretreatment is usually performed in which a component containing a water-soluble polymer such as carboxymethylcellulose or sodium alginate is previously applied to a fabric by a method such as padding (see, for example, Patent Document 2). It is believed that the water-soluble polymer in these fabrics has acted as an ink retaining component (absorbing layer) to prevent bleeding.

  Unlike the ink-jet printing process that can be handled on demand, such a pre-treatment of the fabric requires a certain amount of the amount to be processed in advance in a separate process, which takes time and has a stock of pre-treatment fabrics. In addition, the processing cost is high, which is an obstacle to the spread of inkjet printing.

  Attempts have been made so far to eliminate the pretreatment by applying a functional liquid for suppressing bleeding to the fabric by an ink jet method. For example, Patent Document 3 was heated using a printing ink jet ink set composed of a recording ink containing a reactive dye, a water-soluble organic solvent and water, and a transparent ink containing a water-soluble polymer and an inorganic base. An ink jet textile printing method for printing on a fabric is disclosed. However, as a result of examination by the present inventors, when printing is performed under heating conditions using an ink-jet ink containing a copper phthalocyanine dye as a dye, in a short steam treatment, compared to printing on a pre-treated cloth. It has been found that there are also problems that color spots are likely to appear, ink dots are not sufficiently spread as compared with other colors, and white spots are likely to occur.

JP 2004-359928 A JP-A-6-116880 JP 2010-65209 A

  The present invention has been made in view of the above problems, and a first object of the present invention is to obtain uniform dyeability even in a short time steam treatment, and bleeding between colors (hereinafter, also referred to as coloring bleeding). ) Is suppressed. It is to provide an ink set for textile printing. A second object is to provide an ink set for printing and an ink jet printing method which can suppress bleeding even on a fabric which has not been subjected to pretreatment, and can obtain a high color density without white spots by a short steam treatment. It is in.

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

  1. The ink composition A containing at least a copper phthalocyanine dye, a water-soluble organic solvent and ethylene urea, and the content of the ethylene urea contained in the dye other than the copper phthalocyanine dye, the water-soluble organic solvent and the ink composition A is A mass. %, And an ink composition B containing less than A / 2% by mass (including 0% by mass) of ethylene urea.

  2. 2. The ink set for textile printing according to 1 above, wherein the copper phthalocyanine dye contained in the ink composition A is a reactive dye having a monochlorotriazinyl group.

  3. 3. The ink set for textile printing according to 2 above, wherein the copper phthalocyanine dye contained in the ink composition A is Reactive Blue 15 or Reactive Blue 72.

  4). 4. An inkjet printing method using the printing ink set according to any one of 1 to 3, wherein a functional ink is applied to a fabric, and the surface temperature of the fabric is 40 ° C. or higher and 100 ° C. or lower. And a second step of applying the functional ink to the portion to which the functional ink has been applied using the textile printing ink set.

  5). 5. The ink-jet printing method as described in 4 above, wherein the functional ink contains ethylene urea.

  According to the present invention, it is possible to provide an ink set for textile printing which can obtain a uniform dyeability even with a short steam treatment and a good image quality with suppressed color bleeding. Further, it was possible to provide an ink set for printing and an ink jet printing method in which bleeding is suppressed even on a fabric that has not been pretreated, and a high color density without white spots is obtained by a short steam treatment.

It is the partial schematic which shows an example of a structure of an inkjet textile printing apparatus. It is the partial schematic which shows an example of the other structure of an inkjet textile printing apparatus. It is the partial schematic which shows an example of the other structure of an inkjet textile printing apparatus.

  Hereinafter, the textile printing ink set and the ink jet textile printing method using the same will be described in detail.

《Ink set for textile printing》
In the ink set for textile printing of the present invention, the ink composition A containing at least a copper phthalocyanine dye, a water-soluble organic solvent and ethylene urea, and a dye other than the copper phthalocyanine dye, a water-soluble organic solvent and the ink composition A are contained. When the content of ethylene urea is A mass%, the ink composition B contains less than A / 2 mass% (including 0 mass%) of ethylene urea.

[Copper phthalocyanine dye]
The copper phthalocyanine dye according to the present invention is a compound represented by the following general formula (1).

In the general formula (1), Q represents an arbitrary substituent, a is an integer of 0 to 3, X represents a hydrogen atom, an alkali metal or NH _4, b is an integer of 1 to 3.

  Examples of the substituent represented by Q include a halogen atom, hydroxyl group, cyano group, nitro group, carboxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, Alkoxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamide group, carbamoyl, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted Examples thereof include a carbamoyl group, an amide group, an alkylthio group, an alkenylthio group, an arylthio group, an acyl group, and a monochlorotriazinyl group.

  The copper phthalocyanine dye according to the present invention is not particularly limited as long as it is a compound represented by the general formula (1), but C.I. I. Acid Blue 87, C.I. I. Reactive Blue 15 and C.I. I. Reactive Blue 72 can be mentioned. In particular, C.I. which is a reactive dye having a monochlorotriazinyl group. I. Reactive Blue 15 and C.I. I. The ink containing Reactive Blue 72 is preferably used in cyan dyeing when cotton is used as the fabric, but has a problem that color spots are likely to occur due to the steam time, but for printing having the structure defined in the present invention. The steam time can be shortened by applying the ink set and the ink jet textile printing method.

[Ethyleneurea]
Next, ethylene urea used in the ink composition according to the present invention will be described.

  In the ink set for textile printing of the present invention, one of the ink compositions (hereinafter also simply referred to as ink) is an ink composition A containing at least a copper phthalocyanine dye, a water-soluble organic solvent, and ethylene urea. To do.

  First, the effect of ethylene urea added to the ink composition A will be described.

  As described above, in the textile printing process, the dye is fixed to the fabric by performing a steam treatment in the coloring process after printing. If the steam treatment time is too short, the dye is not sufficiently fixed to the fabric, and uneven coloring spots are generated. This phenomenon is particularly prominent in printed products using an ink composition containing a copper phthalocyanine dye, and there is a problem that color tone unevenness occurs in addition to density unevenness. As a result of intensive studies by the present inventors, it has been found that by adding ethylene urea to an ink composition containing a copper phthalocyanine dye, the steam treatment time required for suppressing colored spots can be significantly shortened.

  About the said effect of this invention, it estimates as follows.

  When the solution absorption spectrum of copper phthalocyanine dye was measured, the ratio of the main absorption peak to the secondary absorption peak changed due to the concentration of the dye and the organic solvent used for dilution (water-soluble organic solvent contained in the ink). Became clear. From this, in the actual textile printing, it was presumed that the spectral reflection characteristics of the dyed part changed with time due to the change of moisture and residual organic solvent in the printed part during steaming.

  Furthermore, as a result of proceeding with the study on the change in spectral absorption characteristics as described above, the peak ratio was changed with respect to the dye concentration and the organic solvent concentration change used for dilution by adding ethylene urea to the solution of the copper phthalocyanine dye. As a result, the inventors have found that it is possible to suppress the change of the above and have reached the present invention.

  That is, by adding ethylene urea to the ink composition, the change in the spectral absorption waveform during the steam process was suppressed, and as a result, a uniform image with no color spots was obtained even with a short steam process. It is interpreted as a thing.

  On the other hand, with respect to other dye species, the effect of slightly improving color spots by the addition of ethylene urea is recognized, but in combination with an ink composition containing at least a copper phthalocyanine dye, a water-soluble organic solvent and ethylene urea, When printing with an ink set containing a dye, a water-soluble organic solvent, and ethylene urea, the copper phthalocyanine dye oozes out at the boundary portion of the image formed by each dye during the steam process, and as a result, a color bleed occurs. It turned out to be.

  As a result of further study on the above problems, as a result of the ink composition having another hue used in combination with the ink composition containing the copper phthalocyanine dye, the copper phthalocyanine dye may or may not contain ethylene urea. It was found that by adding ethylene urea within a range of less than ½ of the ethylene urea content (mass%) in the ink composition A containing ink, it is possible to prevent color bleeding at the boundary portion printed with each ink composition. It was.

  This effect has not yet been clearly interpreted, but is presumed as follows.

  That is, since the solubility of the copper phthalocyanine dye is low, the speed at which the dye is dissolved and diffused is faster than the fixing speed to the fabric, so that it is considered that bleeding occurs. Furthermore, when ethylene urea, which is also used as a solubilizing agent, is present in a high concentration in the print portion of other colors, it is presumed that the dissolution and diffusion rate of the copper phthalocyanine dye is further accelerated, and as a result, bleeding is likely to occur. . The copper phthalocyanine dye and other dye prints effectively suppress the dissolution and diffusion of copper phthalocyanine dyes by increasing the concentration gradient of ethylene urea more than twice, or by not containing ethylene urea in the print part of other dyes. It is interpreted as possible.

  The amount of ethylene urea added to the ink composition A is preferably in the range of 0.5 to 25.0% by mass of the total mass of the ink composition, and more preferably in the range of 1.0 to 18.0% by mass. It is. In this range, the steam time required for uniform dyeing without spots can be greatly shortened, and the color bleeding at the boundary with other colors can be effectively prevented.

[Dyes other than copper phthalocyanine dyes]
Next, a dye other than the copper phthalocyanine dye contained in the ink composition B, which is one of the ink compositions constituting the textile printing ink set of the present invention, will be described.

  As the dye contained in the ink composition B, a reactive dye, an acid dye, a disperse dye, or the like can be used. Although there is no restriction | limiting in particular as content of each dye, For example, as content of a reactive dye, it is preferable that it is 3.0 mass% or more and less than 20 mass%, Furthermore, 5.0 mass% As mentioned above, it is preferable that it is less than 15 mass%. In particular, the content of the reactive dye in the ink having the highest dye concentration (also referred to as dark ink) in the same color aqueous ink is preferably 10% by mass or more and less than 15% by mass.

  Hereinafter, specific examples of dyes other than the copper phthalocyanine dye applicable to the ink composition B according to the present invention will be listed, but the present invention is not limited to these exemplified dyes.

<Reactive dyestuff>
Examples of reactive dyes that can be used in the present invention include azo dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, triphenylmethane dyes, diphenylmethane dyes, and the like.

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

<Acid dye>
As an acid dye applicable to the present invention,
C. I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 67, 72, 73, 79 99, 104, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219219: 1, 220, 230, 232, 235, 241, 242, 246,
C. I. Acid Orange 3, 7, 8, 10, 19, 22, 24, 51, 51S, 56, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140 142, 144, 149, 152, 156, 162, 166, 168,
C. I. Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127, 131 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415,
C. I. Acid Bioreet 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126,
C. I. Acid Green 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109,
C. I. Acid Brown 2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413,
C. I. Acid Black 1, 2, 3, 24, 24: 1, 26, 31, 50, 52, 52: 1, 58, 60, 63, 63S, 107, 109, 112, 119, 132, 140, 155, 172, 187, 188, 194, 207, 222,
<Disperse dye>
As a disperse dye applicable to the present invention,
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 Green 9,
C. I. Disperse Brown 1, 2, 4, 9, 13, 19,
C. I. Disperse Black 1, 3, 10, 24,
Etc.

(Water-soluble organic solvent)
Although there is no restriction | limiting in particular as a water-soluble organic solvent applicable to the ink composition A and the ink composition B which comprise the ink set for textile printing of this invention, The specific example shown below can be given.

  Alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, etc.), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, Dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine) , Morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylene Tolamine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide) and the like.

[Other additives]
In addition to the above-described additives, the ink composition A and the ink composition B constituting the textile printing ink set of the present invention contain various additives within a range that does not impair the object effects of the present invention. Can do.

(Surfactant)
In the ink set for textile printing of the present invention, various surfactants can be used as the surfactant. The surfactant that can be used in the present invention is not particularly limited. For example, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, Examples thereof include polyoxyethylene / polyoxypropylene block copolymers, alkylamine salts, quaternary ammonium salts, silicon surfactants, and fluorine surfactants. In particular, an anionic or nonionic surfactant can be preferably used.

  In the ink set for textile printing of the present invention, the surface tension is preferably adjusted to 30 mN / m or more and 60 mN / m or less. Particularly, by using an acetylene glycol surfactant, the foaming property is relatively low, This is preferable from the viewpoint of adjusting the surface tension and obtaining the emission stability.

  The method for measuring surface tension is described in reference textbooks on general surface chemistry and colloid chemistry. For example, New Experimental Chemistry Course Vol. 18 (Interface and Colloid), edited by the Chemical Society of Japan, Maruzen Co., Ltd. Issue: P.A. 68-117 can be referred to, and specifically, it can be determined using a ring method (Dunoi method), a vertical plate method (Wilhelmy method), or the like. In the present invention, the surface tension was measured using a surface tension meter CBVP type A-3 type (Kyowa Science Co., Ltd.). The viscosity of the ink set for textile printing of the present invention varies in an appropriate range depending on the inkjet head to be applied, but is generally in the range of 1.5 to 20 mPa · s, preferably 3.0 to 15 mPa · s. It is preferable to set it within the range from the viewpoint of emission stability.

  As other additives, preservatives and antifungal agents can be added to the ink in order to maintain long-term storage stability of the ink. Examples of the antiseptic and antifungal agent include aromatic halogen compounds (for example, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL), and the like. Is mentioned. Furthermore, a pH buffering agent, a chelating agent for capturing calcium salts and heavy metals can also be preferably used.

[Fabric]
Examples of the fiber material constituting the fabric or knitted fabric that can be used in the inkjet printing method of the present invention include silk, nylon, wool, acrylic fiber, polyurethane, cotton, hemp, rayon polyurethane, polyester, acetate, and the like. These fibers may be in any form such as woven fabric, knitted fabric, and non-woven fabric.

<Inkjet printing method>
As a general ink-jet printing method, using a cloth that has been pre-processed for ink-jet printing in which a paste component made of a water-soluble polymer such as carboxymethyl cellulose or sodium alginate is applied to the cloth by a method such as padding. A method of printing with an ink jet printer has been used.

  The ink-jet printing method of the present invention is an ink-jet printing method that does not require the pretreatment as described above, and is a first method in which a functional ink is applied to a fabric and the surface temperature of the fabric is heated and dried at 40 ° C to 100 ° C. And a second step of printing with the printing ink set of the present invention on the portion where the functional ink is printed. The load can be reduced.

[Functional ink]
The functional ink used in the ink jet textile printing method of the present invention is characterized in that a liquid containing a hydrotropic agent is applied from an ink jet head to a fabric in order to obtain a sufficient color density in a color developing process by steaming a recording ink image. It is. By adding a hydrotropic agent, particularly when an acid dye or a reactive dye is used for the recording ink, a favorable effect for improving the color developability is exhibited in the steam treatment after printing. Examples of the hydrotropic agent include water-soluble amides, sulfonamides, urea, urea derivatives, and the like. In addition, when an ink composition containing a reactive dye is used, it is preferable to use an alkali compound for the functional ink in order to accelerate the reaction of the reactive dye, and among the alkali compounds, ethylene urea which is difficult to hydrolyze is preferable. .

In order to suppress bleeding of the ink composition that is continuously printed after the functional ink is applied to the fabric, the amount applied as the functional ink is preferably as small as possible, and the function is preferably 5 to 40 ml / m ^2. This is the amount of ink applied. In view of the preferable application amount of the ink composition, the application amount of the hydrotropic agent, and the stability in the functional ink, the amount of the hydrotropic agent added to the functional ink is preferably 2.5 to 40% by mass. A range of 0 to 30% by mass is particularly preferable.

(Water-soluble organic solvent)
In the functional ink according to the present invention, a water-soluble organic solvent is preferably used for the purpose of suppressing clogging or decap due to drying or the like on the nozzle surface of the inkjet head.

  The water-soluble organic solvent that can be used for the functional ink is not particularly limited, and various water-soluble organic solvents can be used for the purpose of adjusting the surface tension and viscosity of the ink. For example, in addition to ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin and the like, alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec- Butanol, t-butanol, etc.), polyhydric alcohols (eg, polyethylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, hexanetriol, thiodiglycol, etc.), glycol ethers (eg, diethylene glycol monobutyl ether, Ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene Recall monomethyl ether), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine) , Polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N- Methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl) Sulfoxide) and the like.

  The addition amount of the water-soluble organic solvent is preferably in the range of 5.0 to 40% by mass with respect to the total mass of the functional ink.

(Inorganic base)
When the ink composition constituting the textile printing ink set of the present invention uses a reactive dye, an alkaline agent is preferably added to the functional ink. The reactive dye binds to and fixes fibers such as cotton and silk, and at this time, the acid is liberated from the reactive dye. The inorganic base acts as a function of accelerating the binding reaction by neutralizing this acid. As a result, the dyeing rate of the reactive dye to the fiber is improved and the color density is increased. By using an inorganic base as a preferred alkali agent, in addition to improving color development, it is possible to more effectively suppress bleeding of the ink composition.

  There are also organic bases as bases, but organic bases have the disadvantages that the above-mentioned effect of suppressing bleeding is weak, and organic bases often have odors, and are not preferred for the effects of the present invention, and inorganic bases are used. It is preferable.

  Preferred inorganic bases include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, ammonium acetate, lithium acetate, Examples thereof include sodium acetate and potassium acetate.

  As the addition amount of the inorganic base, it is preferable to add it in the range of 0.3 molar equivalent / L or more and 2.0 molar equivalent / L or less as the base equivalent.

  In particular, when various inorganic bases were evaluated for precipitation by drying functional inks, it was found that potassium salts are preferable as inorganic bases because they are difficult to precipitate in functional inks. Similarly, acetate is also preferred because it hardly precipitates in the functional ink. Actually, when these inorganic bases are contained in the functional ink, it is preferable because dry clogging in the ink jet head hardly occurs. Potassium salts and acetates may be used alone or in combination with other inorganic bases.

  Functional properties of the functional ink can be adjusted according to the fabric. The viscosity is preferably in the range of 3.0 to 20 mPa · s. The surface tension is preferably in the range of 25-60 mN / m.

  In the case where functional ink is unevenly distributed on the fabric surface and it is desired to enhance surface coloring, it is preferable that the viscosity is 5.0 to 20 mPa · s and the surface tension is 35 to 60 mN / m.

  When it is desired to penetrate the functional ink to the deep part of the fabric, the viscosity is preferably 3.0 to 12 mPa · s, and the surface tension is preferably 20 to 35 mN / m.

  In the inkjet textile printing method of the present invention, in order to adjust the surface tension of the functional ink according to the present invention, a surfactant can be preferably used in addition to the above-mentioned water-soluble organic solvent.

  Although there is no restriction | limiting in particular as surfactant which can be used by this invention, For example, surfactant mentioned by description of the said ink set for textile printing can be used preferably.

(Printing process)
The functional ink according to the present invention is applied directly from the inkjet head to the fabric. The order in which the functional ink and the printing ink set are applied can be arbitrarily selected. For example, after applying the functional ink to the fabric, the method of applying the printing ink set, the function of applying the printing ink set, and the function The method can be selected from a method of applying a functional ink, a method of bidirectionally scanning a functional ink and an ink set for textile printing with an ink jet head arranged in parallel with a carriage, and applying the ink randomly.

  The method of applying the functional ink to the fabric and then applying the ink set for textile printing is the most preferable method for suppressing bleeding. Specifically, an ink jet head for functional ink is arranged on the upstream side in the fabric conveyance direction, and an ink jet head for printing ink set is arranged on the downstream side of the functional ink, and then the ink set for printing. There is a way to print. In this method, there is room for the functional ink to permeate the fabric and further dry, so that the occurrence of bleeding can be most suppressed during recording with the subsequent textile printing ink set.

  In order to promote the drying of the functional ink, an ink jet head for functional ink is arranged on the upstream side in the fabric conveying direction, and the ink jet for printing ink set is arranged on the downstream side of the ink jet head and the coaxial carriage by about one head. Bleeding is suppressed by the method of providing a head and the method of arranging a functional ink and an inkjet head for a printing ink set on two axes and providing a drying zone between the functional ink application position and the printing ink set application position. From the viewpoint of

  On the other hand, a method in which functional ink and textile printing ink set are scanned bi-directionally with an inkjet head arranged in parallel on a coaxial carriage and randomly applied is also preferable because it can reduce the apparatus size.

  The functional ink application region can be arbitrarily selected, and can be applied to the entire region of the fabric, or can be applied only to a specific region, but it suppresses bleeding of the image and has a high density. Since color development is realized, it is preferable to apply only to the image portion to which the textile printing ink set is applied. This has the merit of reducing the consumption of functional ink and lowering the production cost. Also, applying functional ink to a white background is not preferable because it may lead to contamination of the white background. Furthermore, it is also a preferable form that the amount of functional ink is increased or decreased in accordance with the amount of ink set for textile printing. In this case, it is preferable to increase the amount of functional ink applied in accordance with the increase in the amount of ink set for textile printing.

The application amount of the functional ink, as described above, 5.0~40ml / ^{m 2} with respect to the fabric, more preferably be applied in the range of 7.0~20ml / ^{m 2,} exudation suppression chromogenic From the viewpoint of Of course, the application amount of the functional ink can be determined at an arbitrary ratio according to the application amount of the textile printing ink set, and the functional ink need not be applied to the white background where the textile printing ink set is not applied.

  Functional ink can be supplied from one or more inkjet heads. When functional ink is applied from a plurality of inkjet heads, a plurality of types of functional inks having different compositions may be introduced and applied to each inkjet head.

(Fabric heating: first step)
In the ink jet textile printing method of the present invention, the fabric is heated when the functional ink is applied to the fabric. Specific methods of heating include temperature-controllable air or drying means using hot air, drying means using a hot plate, drying means using visible light or far-infrared light, drying means using a heat roller, A drying means using a means for irradiating microwaves can be appropriately selected and used.

  The permeation of the textile printing ink set can be controlled by heating the fabric when the functional ink is applied. In particular, heating is effective when it is desired to improve the print density by increasing the colorant concentration in the vicinity of the surface. In addition, drying of the functional ink is accelerated, which is preferable from the viewpoint of suppressing bleeding.

  In the inkjet printing method of the present invention, when the fabric is heated, the surface of the surface on which the functional ink is printed is heated in the range of 40 ° C. or more and 100 ° C. or less and dried by heating. It is preferable in that it is easy to achieve both improvement of the ink jet and long-term inkjet emission stability. A more preferable heating temperature range is 50 ° C. or higher and 80 ° C. or lower.

(Dye immobilization process)
The ink jet textile printing method of the present invention includes a step of fixing the dye to the fabric by a heating process after discharging the textile printing ink set of the present invention to form an image on the fabric. The pre-dried fabric is preferably subjected to steaming. The conditions may be determined in consideration of the type of fabric and the type of dye, but the humidity is 50 to 100% (more preferably humidity is 80 to 100%) and the temperature is 90 to 120 ° C (preferably 95 to 105 ° C). It is preferable to be placed in the environment for 3 to 120 minutes (preferably 5 to 40 minutes). Further, after that, it is preferable to wash with warm water containing a surfactant (preferably a nonionic surfactant). By performing such post-treatment, a printed matter excellent in color development and fastness can be obtained.

[Inkjet head]
The inkjet head used in the inkjet textile printing method of the present invention can be selected from various methods such as a piezo method, a thermal method, and a continuous method. The piezo method and the continuous method are preferable because they are highly likely to be stably ejected even with an ink containing a polymer material.

[Inkjet printing device]
Hereinafter, the inkjet printing apparatus applicable to the present invention described above will be described with reference to the drawings. However, the present invention is not limited only to the configurations shown in these illustrated drawings.

  FIG. 1 is a partial schematic diagram illustrating an example of the configuration of an inkjet textile printing apparatus.

  In FIG. 1, an adhesive belt of an ink jet textile printing apparatus, a roller 3 for driving the adhesive belt 1, a head 5 for applying functional ink, and a drying means 6 for drying the fabric after applying the functional ink to the fabric P. And only the configuration of the head 7 for applying the textile printing ink set to the fabric P. In the inkjet textile printing apparatus applicable to the present invention, functional ink and textile printing ink set are given in addition. Control means and the like.

  In FIG. 1, reference numeral 1 denotes an adhesive belt which is held by a support roll 2 and a transport roll 3 and has an adhesive means, particularly preferably a base paste, on an endless base belt.

  The fabric P conveyed from the right direction is sandwiched between the nip roll 4 and the adhesive belt 1 and fixed to the adhesive belt 1. Next, after applying the functional ink on the fabric P from the head 5 for discharging the functional ink, by means of blowing a temperature-controllable wind or hot air, the hot air applying means 6 having a fan 6A and a heating element 6B inside, After the applied functional ink is sufficiently dried, it is applied onto the fabric from the printing ink set ejection head 7 to form an image.

  FIG. 2 is a partial schematic diagram illustrating an example of another configuration of the inkjet textile printing apparatus.

  The ink jet printing apparatus shown in FIG. 2 is different from the ink jet printing apparatus shown in FIG. 1 in that the temperature is different between the upstream side of the functional ink discharge head 5 and the downstream side of the head 7 that discharges the printing ink set. It is the structure which added the wind provision means 6. FIG. The fabric P and the adhesive belt 1 are heated by the warm air applying means 6 installed on the upstream side of the head 5 for discharging the functional ink, thereby firmly fixing the fabric P to the adhesive means of the adhesive belt 1. can do. By the warm air applying means 6 provided on the downstream side of the printing ink set discharge head 7, the printing ink set applied to the fabric can be quickly dried.

  FIG. 3 is a partial schematic diagram illustrating an example of another configuration of the inkjet textile printing apparatus.

  The ink jet printing apparatus shown in FIG. 3 is an adhesive belt that holds and conveys the fabric at the position of the functional ink discharge head 5 as a heating means (drying means) in addition to the ink jet printing apparatus shown in FIG. An example is shown in which the hot plate 10 is arranged on the back surface and the back surface of the adhesive belt that holds and conveys the fabric at the position of the printing ink set discharge head 7 so as to contact the belt.

  In addition to the above-described configuration, the inkjet printing apparatus applicable to the present invention includes the type of fabric, the amount of ink set for printing the fabric, the thickness of the fabric, and the average amount of ink set for printing per unit area. Accordingly, a functional ink control unit including a CPU for controlling the functional ink ejection conditions, or a textile printing ink set control unit that controls ejection of each color textile printing ink set according to the set printing conditions is provided.

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

Example 1
<Preparation of ink set for textile printing>
[Preparation of ink set 1 for textile printing]
(Preparation of ink composition A)
C. I. Reactive Blue 72 12.0%
Ethylene glycol 18.0%
Propylene glycol 4.8%
Glycerin 5.0%
Ethyleneurea 2.0%
Acetylene glycol surfactant (Olfin E1010, manufactured by Nissin Chemical)
0.08%
The above additives were sequentially added, mixed, and dissolved, and then finished to 100% with ion-exchanged water to prepare ink composition A. The viscosity of the ink composition A measured after the preparation was 4.0 mPa · s under a measurement condition of 25 ° C., and the surface tension was 44 mN / m.

(Preparation of ink composition B)
C. I. Reactive Yellow95 12.0%
Ethylene glycol 18.0%
Propylene glycol 6.3%
Ethyleneurea non-added glycerin 5.0%
Acetylene glycol surfactant (Olfin E1010, manufactured by Nissin Chemical)
0.08%
The above additives were sequentially added, mixed, and dissolved, and then finished to 100% with ion-exchanged water to prepare ink composition B. The viscosity of the ink composition B measured after the preparation was 4.0 mPa · s under a measurement condition of 25 ° C., and the surface tension was 43 mN / m.

[Preparation of ink sets 2 to 13 for textile printing]
In the preparation of the ink set 1 for textile printing, the additive concentrations of the dye species and ethylene urea used for the preparation of the ink composition A and the ink composition B were changed as shown in Table 1, and each ink composition was further changed. Ink sets 2 to 13 for textile printing were prepared in the same manner except that the viscosity was 4 mPa · s so that the addition concentration of propylene glycol was adjusted. The surface tension of each prepared ink composition was in the range of 40 to 46 mN / m.

  The details of the dye species described in abbreviations in Table 1 are as follows.

(Cyan dye)
C1: C.I. I. Reactive Blue 72
C2: C.I. I. Reactive Blue 15
C3: C.I. I. Acid Blue 87
(Magenta dye)
M1: C.I. I. Reactive Red 24
M2: C.I. I. Reactive Orange 13
(Yellow dye)
Y1: C.I. I. Reactive Yellow 95
Y2: C.I. I. Acid Yellow 79
<< Preparation of pretreatment cloth for print evaluation >>
Pretreatment cloths 1 and 2 for print evaluation were produced according to the following method.

(Preparation of pretreatment cloth 1)
An aqueous solution containing 2.0% sodium alginate, 3.0% sodium hydrogen carbonate and 10% urea is applied to a cotton fabric with a pad (squeezing ratio: 70%) and dried to prepare pre-treated cloth 1. did.

(Preparation of pretreatment cloth 2)
A 30 g / L ammonium sulfate solution was pad-applied to the silk fabric (drawing rate: 80%) and dried to prepare a pretreated fabric 2.

<Preparation of print evaluation sample>
Using the Nassenger-V (droplet amount: 20 ng / drop), each printing ink set prepared above enclosed in an ink pack was mounted, and a solid image of each color was printed adjacently at 540 dpi × 720 dpi. In addition, dpi as used in the field of this invention represents the number of dots per 2.54 cm. A printed matter was prepared using the pretreatment cloth 2 for the textile ink set 12 and the textile ink set 13, and the pretreatment cloth 1 for the other textile ink sets.

[Dye immobilization process]
After the solid image was formed on each fabric, a sample was produced in which the steam treatment time was 10 minutes and 20 minutes under the conditions of 100% humidity and 95 ° C. Further, the final printed matter was obtained by washing and drying with warm water containing a detergent (Senkanol TC, manufactured by Senka Co., Ltd.). However, for ink sets 12 and 13, the detergent used was changed to Senkanol CWN (manufactured by Senka Corporation).

<Evaluation of print>
(Evaluation of color spot resistance)
The above steam treatment is carried out in 10 minutes and 20 minutes, and solid images corresponding to the ink compositions A and B of each printing ink set (a cyan image formed from the ink composition A and a solid image formed from the ink composition B) are formed. The lightness (L ^* ) and hue (a ^* , b ^* ) were measured at any five locations in the other color image. The maximum value of the color difference (ΔE) between the five measurement data was evaluated according to the following criteria. If it was in the range of ◎ to Δ, it was judged that the color spots were not a practical problem.

◎: ΔE is less than 1.0 ○: ΔE is 1.0 or more and less than 1.5 Δ: ΔE is 1.5 or more and less than 2.0 ×: ΔE is 2.0 or more (Evaluation of color bleeding resistance)
The presence or absence of bleeding at the boundary portion of the solid image corresponding to the ink compositions A and B of each ink set was visually observed, and the color bleeding resistance was evaluated according to the following criteria.

◎: No blur is observed. ○: Cyan density looks slightly dark at the boundary, but it is not observed as a blur. △: Slight cyan blur is partially observed, but there is no practical problem. ×: Over the entire boundary area. Table 1 shows the evaluation results obtained as described above.

  As is apparent from the results shown in Table 1, in the printing ink set 5 in which neither the ink composition A nor the ink composition B contains ethylene urea, the coloration spots of the cyan image are remarkable in the steam treatment time of 10 minutes. Slight color spots are observed even when the steam treatment time is 20 minutes. On the other hand, in the ink composition A containing a copper phthalocyanine dye and ethylene urea, it can be seen that no colored spots of a cyan image are generated even when the steam treatment time is 10 minutes. Furthermore, by using the ink composition B containing a dye other than the copper phthalocyanine dye and containing less than ½ (including but not added) ethylene urea added to the ink composition A, color bleeding is suppressed. I understand that. Note that white spots caused by insufficient dot diffusion were not observed in all samples.

Example 2
<Preparation of ink set for textile printing>
[Preparation of ink set 14 for textile printing]
(Preparation of ink composition A)
C. I. Reactive Blue 72 12.0%
Ethylene glycol 18.0%
Propylene glycol 4.2%
Glycerin 5.0%
Ethyleneurea 1.0%
Acetylene glycol surfactant (Olfin E1010, manufactured by Nissin Chemical)
0.08%
PEG6000 (polyethylene glycol 6000, manufactured by NOF Corporation) 1.8%
The above additives were sequentially added, mixed, and dissolved, and then finished to 100% with ion-exchanged water to prepare ink composition A. The viscosity of the ink composition A measured after the preparation was 6.0 mPa · s under a measurement condition of 25 ° C., and the surface tension was 44 mN / m.

(Preparation of ink composition B)
C. I. Reactive Yellow95 12.0%
Ethylene glycol 18.0%
Propylene glycol 5.6%
Glycerin 5.0%
Ethylene urea non-added acetylene glycol surfactant (Olfin E1010, manufactured by Nissin Chemical)
0.08%
PEG6000 (polyethylene glycol 6000, manufactured by NOF Corporation) 1.8%
The above additives were sequentially added, mixed, and dissolved, and then finished to 100% with ion-exchanged water to prepare ink composition B. The viscosity of the ink composition B measured after the preparation was 6.0 mPa · s under a measurement condition of 25 ° C., and the surface tension was 43 mN / m.

[Preparation of ink sets 15-19 for textile printing]
In the preparation of the printing ink set 14, the amount of ethylene urea added was changed as shown in Table 2, and the amount of propylene glycol added was adjusted so that the viscosity of each prepared printing ink set was 6 mPa · s. In the same manner as described above, ink sets 15 to 19 for textile printing were prepared. The surface tension of each ink composition constituting the prepared textile printing ink set was in the range of 40 to 46 mN / m.

<< Preparation of functional ink >>
The following additives were added, mixed and dissolved to prepare a functional ink.

Potassium carbonate 6.0%
Potassium bicarbonate 2.0%
Ethyleneurea 18.0%
Propylene glycol 15.0%
Acetylene glycol surfactant (Olfin E1010, manufactured by Nissin Chemical)
0.05%
PEG 6000 (polyethylene glycol 6000, manufactured by NOF Corporation) 1.5%
The above additives were sequentially added, mixed and dissolved, and then finished to 100% with ion-exchanged water to prepare a functional ink. The viscosity of the functional ink measured after the preparation was 6.0 mPa · s under a measurement condition of 25 ° C., and the surface tension was 44 mN / m.

<Preparation of print evaluation sample>
A print evaluation sample was prepared using the ink jet printing apparatus shown in FIG. In the ink jet textile printing apparatus shown in FIG. 1, a functional ink ejection head 5 and a textile printing ink set ejection head 7 are installed, and hot air application means (drying section) 6 is installed between the heads. Yes. The functional ink ejection head 5 is equipped with four heads, and the textile printing ink set ejection head 7 is equipped with six heads. The fabric P is held between the transport roll 3 and the nip roll 4 and transported in the transport direction shown in the drawing.

  The functional ink prepared above is applied to the functional ink discharge head 5, and the ink composition A and the ink composition B constituting the printing ink set are respectively provided at two positions of the printing ink set discharge head 7. Was loaded.

A cotton cloth is used as the cloth P, and the transported cloth P first uniformly applies functional ink from the functional ink discharge head 5 to the entire surface of the cloth under the condition of 12 ml / m ² , thereby providing hot air applying means ( After drying at 55 ° C. in the drying unit 6, the printing ink set (ink compositions A and B) was discharged from the printing ink set discharge head 7 to record an image. As the recorded image, a cyan single-color solid image was printed with the ink composition A of the textile printing ink set, and a yellow single-color image was printed with the ink composition B adjacent to each other. Each single color image was 100% duty, and the amount of ink composition applied was about 12 ml / m ² .

  Subsequently, the printed matter was produced through the dye fixing step in the same manner as described in Example 1.

<Evaluation of printed materials>
For the evaluation of the print, in the same manner as the method described in Example 1, in addition to the evaluation of the color spot resistance in 10 minutes of the steam treatment and the evaluation of the color bleeding resistance, according to the following method, the white spot resistance is evaluated. Went.

(Evaluation of white spot tolerance)
The cyan solid image and the yellow solid image formed by the above method were observed using a magnifying glass, and the whiteout resistance was evaluated according to the following criteria.

A: No occurrence of white spot failure is observed in all evaluation images. ○: When observed with a loupe, there is a slight white spot in a solid cyan image but it cannot be seen. Δ: Partial white spot in a cyan solid image However, there are many white spots in a solid cyan image. Table 2 shows the results obtained as described above.

  As is apparent from the results shown in Table 2, the image formed according to the ink jet printing method defined in the present invention is superior in coloration spot resistance, color bleeding resistance and white spot resistance to the comparative example. I understand.

DESCRIPTION OF SYMBOLS 1 Adhesive belt 2 Support roll 3 Conveyance roll 4 Nip roll 5 Functional ink discharge head 6 Hot air supply means (drying part)
7 Head for discharging ink set for textile printing 10 Hot plate P Fabric

Claims (5)

  The ink composition A containing at least a copper phthalocyanine dye, a water-soluble organic solvent and ethylene urea, and the content of the ethylene urea contained in the dye other than the copper phthalocyanine dye, the water-soluble organic solvent and the ink composition A is A mass. %, And an ink composition B containing less than A / 2% by mass (including 0% by mass) of ethylene urea.   The ink set for textile printing according to claim 1, wherein the copper phthalocyanine dye contained in the ink composition A is a reactive dye having a monochlorotriazinyl group.   The ink set for textile printing according to claim 2, wherein the copper phthalocyanine dye contained in the ink composition A is Reactive Blue 15 or Reactive Blue 72.   An inkjet textile printing method using the textile printing ink set according to any one of claims 1 to 3, wherein the functional ink is applied to the fabric, and the surface temperature of the textile is 40 ° C or higher and 100 ° C or lower. An ink-jet printing method comprising: a first step of heat-drying under conditions; and a second step of applying the functional ink to a portion to which the functional ink has been applied using the textile printing ink set.   The inkjet printing method according to claim 4, wherein the functional ink contains ethylene urea.

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