JP2019073642A - Inkjet textile printing ink and inkjet textile printing method - Google Patents

Abstract

To provide an inkjet textile printing ink capable of suppressing changes in tones due to twisting of fibers without reducing a surface density.SOLUTION: The inkjet textile printing ink comprises a reactive dye or an acidic dye, a first acetylene glycol surfactant, a second acetylene glycol surfactant, ethylene urea and water, satisfying expression (1): 4≤h2-h1≤7, where h1 represents an HLB value of the first acetylene glycol surfactant and h2 represents an HLB value of the second acetylene glycol surfactant.SELECTED DRAWING: None

Description

  The present invention relates to an inkjet printing ink and an inkjet printing method.

  An ink jet printing method which does not require plate making is known as one of printing methods corresponding to shortening of delivery time and multi-variety production. The ink jet textile printing method is a method in which minute droplets of ink are ejected from an ink jet recording head and landed on a recording medium to be printed to form an image. In general, the ink jet printing method comprises the steps of: discharging ink from an ink jet head to land on a fabric; and applying steam to the fabric on which the ink is landed to fix the dye contained in the ink on the fibers of the fabric. And. Such an ink jet printing method can form a high definition, high definition image with a relatively simple mechanism, low cost, and high quality.

  Types of coloring materials used in ink jet printing inks include acid dyes, disperse dyes, reactive dyes, and the like, which are selected according to the type of fabric. For example, reactive dyes may be used for image formation on a cellulose-based fabric.

  As an ink jet printing ink containing a reactive dye, Patent Document 1 discloses an ink jet printing ink containing a reactive dye, urea, 2-imidazolidinone, and an organic buffer.

JP, 2010-116566, A

  However, the fabric on which an image is formed by the ink jet printing method using the conventional ink jet printing ink as shown in Patent Document 1 is, for example, a portion of the twisted portion when fibers on the surface are twisted due to friction during washing. There was a problem that the color tone was lightened and in severe cases it turned white. Such a change in color tone due to fiber twisting is considered to be caused by the fact that the fibers on the surface of the fabric are twisted and moved to expose the ink-impeded back portion of the fibers on the surface of the fabric. That is, the ink penetrates only to the front side (on which ink droplets land) of the fibers on the surface of the fabric, and does not penetrate to the back side, so it is considered that the color tone changes due to twisting. .

  Therefore, in order to suppress the change in color tone due to fiber twisting, it is considered effective to make the ink easily penetrate to the inside of the fabric. However, when the ink is made to easily penetrate into the inside of the fabric, the ink is less likely to stay on the surface of the fabric, and there is a problem that the surface concentration of the fabric is easily reduced.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an ink jet textile printing ink capable of suppressing a change in color tone due to fiber twisting without reducing the surface concentration of the fabric.

[1] A reactive dye or an acid dye, a first acetylene glycol surfactant, a second acetylene glycol surfactant, ethylene urea, and water,
An inkjet textile printing ink satisfying the following formula (1), where h1 is the HLB value of the first acetylene glycol surfactant and h2 is the HLB value of the second acetylene glycol surfactant.
Formula (1): 4 ≦ h2-h1 ≦ 7
[2] The inkjet textile printing ink according to [1], wherein the h1 is 6 or more and 12 or less, and the h2 is 10 or more and 19 or less.
[3] The content mass ratio of the first acetylene glycol surfactant and the second acetylene glycol surfactant is the same as the first acetylene glycol surfactant / the second acetylene glycol surfactant interface. The inkjet textile ink according to [1] or [2], wherein the activator is 6/4 to 2/8.
[4] The total content of the first acetylene glycol surfactant and the second acetylene glycol surfactant is 0.03% by mass or more and 2% by mass with respect to the total mass of the inkjet textile ink. The inkjet textile printing ink as described in any one of [1]-[3] which is the following.
[5] The inkjet textile printing ink according to any one of [1] to [4], wherein the content of the ethylene urea is 1% by mass to 15% by mass with respect to the total mass of the inkjet textile printing ink .
[6] The inkjet textile printing ink according to any one of [1] to [5], wherein the content of the reactive dye is 20% by mass or more and 40% by mass or less based on the total mass of the inkjet textile printing ink .
[7] The inkjet textile printing ink according to any one of [1] to [5], wherein the content of the acid dye is 7% by mass to 15% by mass with respect to the total mass of the inkjet textile printing ink.
[8] An ink jet printing method, comprising the steps of: discharging droplets of the ink jet printing ink according to any one of [1] to [7] from an ink jet recording head to form an image on a fabric.
[9] The inkjet textile printing method according to [8], wherein the fabric comprises cellulose fiber or protein fiber.
[10] The inkjet textile printing method according to [8] or [9], wherein the inkjet recording head is a line head.

  ADVANTAGE OF THE INVENTION According to this invention, the inkjet textile printing ink which can suppress the change of the color tone by fiber twisting can be provided, without reducing the surface concentration of a fabric.

It is a partial schematic diagram showing an example of composition of an ink jet textile printing apparatus.

  The present inventors combine a first acetylene glycol surfactant having a low HLB value with a second acetylene glycol surfactant having a high HLB value, and set the difference between the HLB values to a certain value or more, In addition, it has been found that by using an ink containing ethylene urea, it is possible to suppress a change in color tone due to fiber twisting without reducing the surface concentration of the fabric.

Although the reason for this is not clear, it is considered as follows.
1) First, because ethylene urea contained in the ink has a small molecular weight, when the ink lands, it tends to appear on the ink droplet surface faster than the surfactant, and the surface tension of the ink droplet surface becomes high. Therefore, ink droplets that have landed on the fabric do not penetrate the fabric immediately after landing, and tend to stay on the surface of the fabric.
2) Then, as time passes, first, the first acetylene glycol surfactant having a small molecular weight in the acetylene glycol surfactant diffuses and comes out on the surface of the ink liquid. Thereby, the surface tension of the ink droplet is reduced, and the penetration of the ink into the fabric is promoted.
3) When time passes further, a second acetylene glycol surfactant having a larger molecular weight among the acetylene glycol surfactants comes out on the surface of the ink droplet, so the surface tension of the ink is increased, and the ink Permeation to the fabric is delayed. As a result, the ink tends to accumulate inside the fabric, so that not only the ink can wrap around to the back side of the fiber, but also the ink remaining on the surface of the fabric gradually penetrates into the fiber.

  That is, the penetration speed of the ink into the fabric after being landed on the fabric is changed with time. Specifically, after the ink is allowed to stay on the fabric (see 1), first, the penetration rate of the ink is increased (see 2), and the penetration rate of the ink is reduced halfway (3) reference). As a result, at first, the penetration speed of the ink is fast, so the ink rapidly penetrates in the vicinity of the surface of the fabric, but since the penetration speed of the ink gradually decreases halfway, the ink tends to be accumulated inside the fabric. As a result, the ink can be sufficiently circulated and penetrated not only on the front side of the fiber (the side on which the ink droplets land) but also on the back side near the surface of the fabric. As a result, since the ink can be sufficiently permeated to both the front side and the back side of the fiber in the vicinity of the surface of the fabric, it is possible to suppress the change in color tone due to fiber twisting without reducing the surface concentration. it is conceivable that. The present invention has been made based on such findings.

1. Ink Jet Textile Ink The ink jet textile ink of the present invention contains a reactive dye or an acid dye, a first acetylene glycol surfactant, a second acetylene glycol surfactant, ethylene urea, and water. The ink jet printing ink of the present invention may further contain a water-soluble organic solvent, other additives, etc., as required.

1-1. Reactive dye or acid dye (reactive dye)
The reactive dye may be either a reactive dye having a vinyl sulfone group (hereinafter also referred to as a vinyl sulfone type reactive dye) or a reactive dye having a monochlorotriazine group (hereinafter also referred to as a monochlorotriazine type reactive dye). From the viewpoint of achieving the effects of the present invention, vinyl sulfone type reactive dyes capable of dyeing at higher concentrations are preferable.

The vinyl sulfone type reactive dye produces the following reaction in the presence of an alkali.
_{D-SO 2 -CH 2 CH 2} -O-SO 3 M (1)
D D-SO ₂ CH = CH ₂ + HO-SO ₃ M (1 ')

  D of Formula (1) represents a dye matrix. Examples of the dye base include pyrazolone azo type, γ acid azo type, H acid azo type, anthraquinone type, and H acid disazo type. M of Formula (1) represents a monovalent metal cation. Examples of monovalent metal cations include Na ion.

  In the vinyl sulfone type reactive dye, the vinyl group generated from the vinyl sulfone type reactive dye undergoes a nucleophilic addition reaction to the hydroxyl group of the fabric to react with the fabric.

  The reactive dye has one or more vinyl sulfone groups. The reactive dye may have two functional groups that react with the fabric from the viewpoint of enhancing the dyeability to the fabric, but at least one of the two or more functional groups may be a vinyl sulfone group. . The bifunctional reactive dye having two reactive functional groups includes a reactive dye having two vinyl sulfone groups in one molecule (hereinafter, also referred to as a vinyl sulfone type homobifunctional reactive dye), and one in one molecule. Included are reactive dyes having a vinyl sulfone group and one monochlorotriazine group (hereinafter also referred to as heterobifunctional reactive dyes). The reactive dye having a vinylsulfone group used in the present invention is preferably a vinylsulfone type homobifunctional reactive dye from the viewpoint of further improving the dyeability to a fabric.

  When a hetero-bifunctional reactive dye is used as the reactive dye, the reaction of the reactive dye with the fabric may cause not only the above-mentioned nucleophilic addition reaction but also a nucleophilic substitution reaction. This results from the nucleophilic substitution reaction of the chloro group of the monochloro-substituted 1,3,5-triazin-2-yl skeleton possessed by the heterobifunctional reactive dye with the hydroxyl group of the fabric.

  Examples of reactive dyes having a vinyl sulfone group include C.I. I. Reactive Yellow 15, C.I. I. Reactive Yellow 37, C.I. I. Reactive yellow 42; C.I. I. Reactive Orange 16, C.I. I. Reactive Orange 74, C.I. I. Reactive orange 107; C.I. I. Reactive red 23, C.I. I. Reactive red 35, C.I. I. Reactive red 106, C.I. I. Reactive red 180, C.I. I. Reactive red 218; C.I. I. Reactive Violet 5, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 21, C.I. I. Reactive Blue 38, C.I. I. Reactive blue 229; C.I. I. Reactive Brown 18; C.I. I. Reactive Black 5, C.I. I. Reactive Black 14, C.I. I. Reactive black 31 and the like are included. Among these, C.I. I. Reactive black 5 is preferred.

(Acid dye)
The acid dye is a dye having an acid group in the molecule. Examples of the acidic group include a sulfone group and a carboxyl group.

Examples of acid dyes are
C. I. Acid Yellow 1,3,11,17,18,19,23,25,36,40,40: 1,42,44,49,59,59: 1,61,65,67,72,73,79 99, 104, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219, 1, 220, 230, 232, 235, 241, 242, 246,
C. I. Acid Orange 3, 7, 8, 10, 19, 22, 22, 24, 51, 51 S, 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, 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, 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 Violett 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 97, 102, 109, 126,
C. I. Acid Blue 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127: 1 , 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350,
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, 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 and the like.

  The reactive dye or the acid dye content is based on the total mass of the ink in the reactive dye, from the viewpoint of increasing the image density, and the viewpoint of easily obtaining the effect of the present invention that the change in color tone due to fiber twisting can be suppressed. 20 to 40 mass%, and in the case of the acid dye, it is preferably 7 to 15 mass%.

1-2. Acetylene Glycol Surfactant The first acetylene glycol surfactant and the second acetylene glycol surfactant may be alkylene oxide adducts of an acetylene glycol compound.

  The bonding site of the alkylene oxide group in the alkylene oxide adduct of the acetylene glycol compound is not particularly limited, but is preferably bonded to at least one hydroxy group of the glycol moiety, and more preferably bonded to both hydroxy groups.

That is, the first acetylene glycol surfactant and the second acetylene glycol surfactant are preferably represented by the following formula (I).

R ¹ and R ^{2 in} General Formula (I) each independently represent an alkyl group having 1 to 5 carbon atoms. The alkyl group may have a linear structure or a branched structure. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group Can be mentioned. R ¹ and R ² may be the same or different.

R ^{3 in the} general formula (I) independently represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group include ethylene group and propylene group, preferably ethylene group.

  Each of m and n in the general formula (I) represents the number of added moles of alkylene oxide. The m and n of the first acetylene glycol surfactant and the second acetylene glycol surfactant may be set such that the HLB value is in the range described later. For example, when the alkylene oxide is ethylene oxide, m and n are set according to the HLB value in the range of 0.5 to 25 and m + n is set according to the HLB value in the range of 1 to 50, for example It can be done.

When the HLB value (Hydrophilic-Lipophilic Balance) of the first acetylene glycol surfactant is h1, and the HLB value of the second acetylene glycol surfactant is h2, the following formula (1) is satisfied.
Formula (1): 4 ≦ h2-h1 ≦ 7

  Formula (1) indicates that the surface tension of the first acetylene glycol surfactant is moderately low, and the surface tension of the second acetylene glycol surfactant is moderately high. The first acetylene glycol surfactant having an appropriately low surface tension has a small amount of ethylene oxide added and a small molecular weight, so the diffusion speed in the ink is high. On the other hand, the second acetylene glycol surfactant having an appropriately high surface tension has a large addition amount of ethylene oxide and a large molecular weight, so the diffusion speed in the ink is low.

  The droplet of the ink containing such an acetylene glycol surfactant is landed on the fabric, and when time passes, the first acetylene glycol surfactant having a small molecular weight first diffuses, and the ink droplet Unevenly distributed on the surface of Thereby, the surface tension of the ink droplet is reduced, and the penetration of the ink into the fibers is promoted. Thereafter, when time passes further, the second acetylene glycol surfactant having a large molecular weight diffuses and is likely to be unevenly distributed on the surface of the ink. Thereby, the surface tension of the ink is increased, and the penetration of the ink into the fabric is delayed. As a result, the ink tends to accumulate inside the fabric, so that not only the ink can wrap around to the back side of the fiber, but also the ink remaining on the surface of the fabric gradually penetrates into the fiber. As a result, since the ink can sufficiently penetrate both the front side and the back side of the fiber in the vicinity of the surface of the fabric, it is possible to reduce the change in color tone due to fiber twisting without reducing the surface concentration. .

  The HLB value (h1) of the first acetylene glycol surfactant is preferably 6 or more and 12 or less, and more preferably 7 or more and 11 or less.

  The HLB value (h2) of the second acetylene glycol surfactant is preferably 10 or more and 19 or less, and more preferably 11 or more and 16 or less.

The HLB value is a value which is defined by the following equation by the Griffin method (J. Soc. Cosmetic Chem., 5 (1954), 294) and is obtained by arithmetic.
HLB value = 20 × sum of formula weight of hydrophilic part / molecular weight (i)
The hydrophilic portion indicates, for example, an alkylene oxide group.

  The HLB value of the first acetylene glycol surfactant and the second acetylene glycol surfactant can be adjusted, for example, by the addition amount of alkylene oxide. For example, when the HLB value is increased, the addition amount of alkylene oxide may be increased, and when the HLB value is decreased, the addition amount of alkylene oxide may be reduced.

  The mass ratio of the first acetylene glycol surfactant to the second acetylene glycol surfactant (first acetylene glycol surfactant / second acetylene glycol surfactant) is 6/4 to 4 It is preferably 2/8, more preferably 5/5 to 2/8, and still more preferably 4/6 to 2/8. By setting the content mass ratio of the second acetylene glycol surfactant to a certain level or less, the penetration of the ink does not become too slow, so the ink can more easily penetrate into the inside of the fabric, and the change in color tone due to fiber twisting It can be less. By setting the content mass ratio of the first acetylene glycol surfactant to a certain value or less, the penetration of the ink is not promoted too much, so the ink can be more easily accumulated inside the fabric, and the color tone due to fiber twisting Change can be less.

  The total content of the first acetylene glycol surfactant and the second acetylene glycol surfactant is preferably 0.03% by mass or more and 2% by mass or less with respect to the total mass of the ink.

  The first acetylene glycol surfactant and the second acetylene glycol surfactant may be contained alone or in combination of two or more. For example, when two or more types of second acetylene glycol surfactants are contained, the content of the second acetylene glycol surfactants is the total amount of two or more types of second acetylene glycol surfactants. Do.

1-3. Ethylene urea Ethylene urea has a hydrophobic site consisting of -CH ₂ -CH ₂ -and a hydrophilic site consisting of -NH-CO-NH-. In the ink, since the hydrophobic portion of ethylene urea is easily compatible with the reactive dye and the acid dye, the hydrophilic portion on the opposite side is easily oriented to the surface of the ink, whereby the surface tension of the ink can be increased. Thereby, the penetration of the ink into the fabric can be delayed, and the ink can be easily accumulated on the surface or inside of the fabric.

  The content of ethylene urea is preferably 1% by mass to 15% by mass with respect to the total mass of the ink. When the content of ethylene urea is 1% by mass or more, the penetration of the ink into the fabric is easily delayed, and the ink may be easily accumulated on the surface or the inside of the fabric. Therefore, the fiber concentration is maintained while further maintaining the surface concentration. It is easy to suppress the change in color tone. When the content of ethylene urea is 15% by mass or less, the penetration of the ink into the fabric is not too slow, so the ink can easily penetrate into the inside of the fabric, and the change in color tone due to fiber twisting can be further suppressed. The content of ethylene urea is more preferably 4% by mass or more and 12% by mass or less based on the total mass of the ink.

1-4. Water-soluble organic solvent The ink jet printing ink of the present invention may further contain a water-soluble organic solvent. The water-soluble organic solvent is not particularly limited as long as it can dissolve the reactive dye and the acid dye.

Examples of water soluble organic solvents are
Alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol);
Polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 2, 2 -Thiodiethanol);
Amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyl Diethylene triamine, tetramethyl propylene diamine);
Amides (for example, N, N-dimethylformamide, N, N-dimethylacetamide and the like);
Heterocycles (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, etc.);
Sulfoxides (eg, dimethyl sulfoxide) and the like are included.

1-5. Other Additives The ink jet printing ink of the present invention further contains other additives such as pH adjusters, surfactants other than acetylene glycol surfactants (other surfactants), preservatives, fungicides, etc. May be.

[PH adjuster]
Examples of pH adjusters include urea, sodium hydroxide and the like. Among them, urea is preferable because it is easy to maintain the pH of the ink in a predetermined range by using it in combination with a reactive dye having acid release property since it has alkali release property.

  The content of the pH adjuster is preferably 1 to 10% by mass with respect to the total mass of the ink. When the content of the pH adjuster is 1% by mass or more, the pH of the ink is easily stabilized, and when it is 10% by mass or less, for example, when urea is used, it is attributed to decomposition of urea under long-term storage. Since thickening of the ink is also less likely to occur, long-term storage stability is also less likely to be impaired. The content of the pH adjuster is more preferably 2 to 5% by mass with respect to the total mass of the ink.

[Other surfactant]
Examples of other surfactants include dialkyl sulfosuccinates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, alkylamine salts , Quaternary ammonium salts, silicon surfactants, or fluoro surfactants.

[Antiseptic, antifungal agent]
Examples of preservatives and fungicides include aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, 1,2-benzisothiazolin-3-one (eg, PROXEL GXL), etc. Is included. Preservatives and fungicides enhance the storage stability of the ink.

1-6. Physical Properties of Ink The ink jet printing ink of the present invention preferably has an ink viscosity of 1 to 100 mPa · s at 25 ° C., and more preferably 1 to 40 mPa · s, from the viewpoint of ejection from the ink jet recording head. And 5 to 40 mPa · s are more preferable, and 5 to 20 mPa · s is particularly preferable. The viscosity of the ink can be measured by a cone-plate viscometer, for example, a TVE-33LT viscometer manufactured by Toki Sangyo Co., Ltd.

1-7. Preparation of Ink The ink jet printing ink of the present invention is required to have the above-mentioned reactive dye or acid dye, a first acetylene glycol surfactant, a second acetylene glycol surfactant, ethylene urea and water. And mixing with other ingredients depending on the situation.

2. Ink jet textile printing method The ink jet textile printing method of the present invention includes the step of discharging droplets of the ink jet textile printing ink of the present invention from an ink jet recording head to form an image on a fabric.

  Specifically, in the inkjet printing method of the present invention, (1) a step of applying a pretreatment agent to the fabric (pretreatment step), and (2) droplets of the printing ink on the fabric to which the pretreatment agent is applied And (3) heat the fabric on which the image is formed to fix the image on the fabric (coloring step), as necessary 4) A step of drying the fabric after ink application (preliminary drying step), (5) a step of removing a dye and pretreatment agent which could not be dyed onto the fabric (washing step), and (6) a washed fabric And drying (drying step).

2-1. Pretreatment Step The pretreatment step is a step of applying a pretreatment agent to the fabric. Examples of methods for applying the pre-treatment agent to the fabric include a pad method, a coating method, a spray method, and an inkjet method. Pretreatment agents can be applied onto fabrics by these methods. Examples of the fabric to which the pre-treatment agent is applied include a fabric having an ink receiving layer described in JP-A-62-53492 and a reduction inhibitor and an alkali agent described in JP-B-3-46589. Included are fabrics and the like.

  From the viewpoint of obtaining a uniform image, before applying the pre-treatment agent to the fabric, natural impurities (oil, fat, wax, pectin, natural pigment, etc.) attached to the fabric fibers, residues of drugs used in the fabric manufacturing process ( It is preferable to wash away a paste, etc., or dirt and the like attached to the fabric. The detergent for washing the fabric includes an alkaline agent such as sodium hydroxide or sodium carbonate, an anionic or nonionic surfactant, an enzyme or the like.

  When an ink jet printing ink containing a reactive dye is used, the pretreatment agent preferably contains at least a resin component, an alkali agent, and a hydrotrope agent.

  The resin component preferably contains a hydrophilic resin (preferably a hydrophilic resin having a hydroxy group). Examples of hydrophilic resins include natural gums such as guar and locust bean, starches, seaweeds such as sodium alginate and fusori, plant hides such as pectic acid, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose Fibrin derivatives such as roasted starch, modified starch such as roasted starch, alpha starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch etc., processed natural gum such as Shiratsu gum system, roast bean gum system, algin derivative, polyvinyl alcohol, poly Synthetic glue such as acrylic ester, emulsion and the like are included.

  Examples of alkali agents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as mono, di and triethanolamine, and carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate (sodium hydrogen carbonate). Or alkali metal salts of bicarbonates, metal salts of organic acids such as calcium acetate and barium acetate, ammonia and ammonia compounds, sodium trichloroacetate which becomes an alkali agent under steaming or dry heat, and the like. Among these, sodium carbonate and sodium hydrogen carbonate are preferable. It is preferable that it is 0.1-10 mass% with respect to the total mass of a fabric, and, as for the provision amount of an alkaline agent, it is more preferable that it is 0.5-5 mass%. The presence of a suitable alkali agent in the fabric ensures that the printing ink containing the reactive dye can be dyed. Therefore, it is preferable to make the cloth contain an alkaline agent in advance.

  When using an ink jet printing ink containing an acid dye, the pre-treatment agent preferably contains at least the above-mentioned resin component and a pH adjuster.

  The pH adjuster is more preferably an acid from the viewpoint of facilitating formation of a clear image with high density. Examples of pH adjusters that are acids include citric acid, malic acid and tartaric acid.

  These pretreatment agents may further contain a reduction inhibitor, preservative, or chelating agent, as required. Examples of the reduction inhibitor include sodium m-nitrobenzene sulfonate and the like. The preservative may be a preservative exemplified as a preservative of ink jet printing ink, or may be the same. Examples of the chelating agent may be ethylenediamine tetraacetate, nitrilotriacetate, hexametaphosphate, pyrophosphate or metaphosphate.

  The amount of application of the pre-treatment agent (reduction of area) or the amount of the resin component contained in the pre-treatment agent is appropriately set according to the type of fabric and its use.

  The pretreatment agent applied to the fabric can also be heat dried using warm air, a hot plate, or a heat roller.

  The fiber material constituting the fabric is not limited as long as it is a fiber that can be dyed by the ink jet printing ink of the present invention.

  When an ink jet printing ink containing a reactive dye is used, the fabric is not particularly limited as long as a hydrophilic resin having a hydroxy group or an amino group is provided as a pretreatment agent. The fabric preferably contains a reactive dyeable fiber, for example, a cellulose fiber such as cotton, or a protein fiber such as silk, from the viewpoint of enhancing dyeability. The fabric may be any of these fibers such as woven fabric, non-woven fabric and knitted fabric. Also, the fabric may be composed of only fibers that can be dyed with a reactive dye, but it may be a blended woven or blended non-woven fabric with rayon, polyurethane, polyester, or acrylic.

  When an ink jet printing ink containing an acid dye is used, the fabric preferably contains a fiber containing cotton, hemp, wool, silk, rayon, vinylon, nylon, acrylic, polyurethane, polyester or acetate. The fabric may be any of these fibers such as woven fabric, non-woven fabric and knitted fabric. Also, the fabric may be composed of only fibers that can be dyed with acid dyes, such as wool, silk or nylon-based fibers, from the viewpoint of causing acid dyes to color well, but mixed weave with other fibers It may be a cloth or a blended non-woven fabric or the like.

  It is preferable that the thickness of the fiber which comprises a cloth exists in the range of 10-100 d.

2-2. Ink Application Process The ink application process is a process of forming droplets of ink jet printing ink from the ink jet recording head toward the fabric to form an image before color development. Droplets of the ink jet textile ink set are ejected to land on the cloth while moving the cloth relative to a head carriage on which a plurality of ink jet recording heads are mounted.

  The ink application process is preferably performed by a line head type ink jet textile printing apparatus using a line head as an ink jet recording head. That is, in a scan head type ink jet printing apparatus using a scan head as an ink jet recording head, since droplets are deposited a plurality of times at one location, the droplets of the ink deposited and the droplets of the newly deposited ink are deposited. Since mutual adsorption tends to work between the surfaces, the surface concentration tends to rise, and the ink tends to penetrate to the back side of the fiber. On the other hand, in the line head type ink jet textile printing apparatus, since the above-described mutual adsorption does not work because the ink droplets are ejected only once at one place, the surface concentration is difficult to increase and the ink hardly penetrates to the back side of the fiber. In the present invention, even in the case of forming an image with a line head type ink jet printing apparatus, by using the ink jet textile printing ink of the present invention, the ink can be easily permeated to the back side of the fiber while increasing the surface density. It is possible to reduce the change in color tone due to twisting.

  The ejection frequency by the line head is preferably 10 to 300 kHz.

  The surface temperature of the fabric when the ink droplets land is not particularly limited, but is preferably heated in the range of 35 to 70 ° C. from the viewpoint of suppression of bleeding of the image before color development and the like. The ink temperature is preferably kept at 25 ° C. from the viewpoint of suppressing the fluctuation of the ink viscosity due to the fluctuation of the ink temperature.

2-3. Preliminary Drying Step The preliminary drying step is a step of drying the ink-applied fabric. Although not particularly limited, pre-drying is preferred to dry the fabric at 150 ° C. or less for 0.5 to 30 minutes. Examples of the drying method include an air convection method, a heating roll direct attachment method, and an irradiation method. Specifically, the ink may be applied to the fabric, and the fabric may be dried under the above conditions and method before the fabric is wound up.

2-4. Coloring step In the coloring step, the fabric after application of ink (after preliminary drying when including the preliminary drying step) is heated to dye reactive dye or acid dye not sufficiently dyed in the fabric into the fabric. And the step of expressing the original hue of the ink.

  The coloration temperature (heating temperature) is preferably 95 ° C. or more and less than 220 ° C., from the viewpoint of strengthening the dyeing of the reactive dye or the acid dye on the fabric, although it depends on the coloration method (heating method). It is more preferable that the temperature is not less than ° C and not more than 190 ° C, and further preferably not less than 100 ° C and not more than 180 ° C.

  The coloring method (heating method) may be a conventionally known method, and is appropriately selected depending on printing ink and fabric. For example, steam steaming; baking by dry heat, thermosol; HT steamer by superheated steam, and the like. Among them, a system (steaming system) and a dry heat system (baking system) in which the reactive dye or the acid dye in the ink is fixed by the high heat vapor are preferable.

  In the steaming system using high temperature steam, when the heating temperature is too low, a large amount of liquid water is present, for example, the reactive dye contained in the ink tends to hydrogen bond with the liquid water other than the fabric, so It may be washed away and may not be dyed sufficiently. Therefore, for example, from the viewpoint of strengthening the dyeing of the reactive dye on the fabric, the heating temperature is preferably 95 ° C. or higher, and more preferably 100 ° C. or higher. For example, cellulose fibers are preferably treated at 95 to 105 ° C. for 5 to 15 minutes; amide fibers such as silk or wool are preferably treated at 95 to 105 ° C. for 20 to 40 minutes . In addition, the fabric to which the ink is applied may be colored immediately, or may be colored after a lapse of time.

  In the baking method using dry heat, the heating temperature is preferably 150 ° C. or more and less than 220 ° C., preferably 150 ° C. or more and 190 ° C., from the viewpoint of easily obtaining sufficient dyeability and suppressing decomposition of the dye. The temperature is more preferably 150 ° C. or more and 180 ° C. or less.

2-5. Washing Step The washing step is a step of removing the reactive dye or acid dye or pretreatment agent that could not be dyed onto the fabric after the coloration step of the fabric. The removal of the reactive dye or the acid dye which can not be dyed onto the fabric can be carried out using a conventionally known washing method, and is appropriately selected depending on the printing ink, the fabric and the like. For example, cellulose fibers are generally washed with water and hot water and then treated with a soaping bath containing a nonionic detergent, followed by washing with water and washing with water. Removal of undyed reactive dye or acid dye tends to improve the washing fastness, water fastness and sweat fastness. If there is a reactive dye or acid dye which can not be dyed to the fabric, it is difficult to obtain washing fastness, water fastness and sweat fastness.

2-6. Drying Step The drying step is a step performed after the washing step to dry the washed fabric. The drying method is not particularly limited, and may be a method of squeezing, drying or drying the washed fabric using a dryer (heat roll, iron, etc.).

2-7. Ink Jet Textileing Apparatus Hereinafter, an apparatus for performing the ink application process and the preliminary drying process will be described with reference to the drawings, but the inkjet textile printing apparatus is not limited thereto.

  FIG. 1 is a partial schematic view showing an example of the configuration of an ink jet printing apparatus. The inkjet textile printing apparatus includes a transport means 2 for transporting the fabric P, a head carriage 5 carrying a plurality of inkjet recording heads (not shown) for discharging droplets of the inkjet textile ink onto the fabric P, and warm air on the fabric P. And warm air applying means 6 for applying.

  The conveyance means 2 includes an adhesive belt 21, a support roller 22, a conveyance roller 23, and a nip roller 24. The adhesive belt 21 is held by the support roller 22 and the conveyance roller 23, and circulates between the support roller 22 and the conveyance roller 23. The nip roller 24 is disposed to face the transport roller 23 via the adhesive belt 21.

  The head carriage 5 and the warm air application means 6 are disposed above the fabric P.

  The head carriage 5 is provided with an ink jet recording head. The type of the inkjet recording head is not particularly limited, and may be either thermal or piezo. The nozzle diameter of the inkjet recording head is preferably 10 to 100 μm, and more preferably 10 to 50 μm. When the nozzle diameter is 10 μm or more, nozzle clogging due to the insoluble matter hardly occurs, and when the nozzle diameter is 100 μm or less, the sharpness of the formed image is hardly deteriorated. The droplet size of the ink to be ejected is preferably 4 to 150 pl, more preferably 5 to 80 pl. When the droplet size of the ink is 4 pl or more, the ejected ink droplet is less susceptible to the air flow near the head, and when it is 150 pl or less, the graininess of the formed image is less noticeable.

  The inkjet recording head may be a scan head (serial head) or a line head. Among them, the inkjet recording head is preferably a line head, from the viewpoint of high image formation speed and easy to obtain the effects of the present invention.

  The warm air application means 6 includes a fan 6A for blowing air onto the fabric and a heating element 6B capable of controlling the temperature.

  When the transport roller 23 is driven, the fabric P disposed on the upper surface of the adhesive belt 21 is transported to the lower surface of the nip roller 24. The fabric P is pressed by the adhesive belt 21 and the nip roller 24 and fixed to the adhesive belt 21. The fabric P fixed to the adhesive belt 21 is conveyed below the head carriage 5. The plurality of ink jet recording heads mounted on the head carriage 5 discharge droplets of ink jet textile printing ink, and land them on a predetermined area (landable area) of the fabric to which the pretreatment agent is applied to form an image. Next, the temperature-controlled air or warm air is blown from the warm air application unit 6 to dry the image formed on the fabric P.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

1. Ink Material (1) Reactive Dye Reactive Black 5
Reactive Red 218

(2) Acid dye C.I. I. Acid Black 52

(3) First acetylene glycol surfactant / second acetylene glycol surfactant: Ethylene oxide is added to the acetylene glycol compound represented by the following formula by an existing method to obtain ethylene oxide of acetylene glycol compound The adduct was synthesized.

  The ethylene oxide adduct of the obtained acetylene alcohol was fractionated by GPC to obtain ethylene oxide adducts AG1-8 of an acetylene glycol compound shown in Table 1.

  The HLB value of ethylene oxide adducts AG1-8 of the obtained acetylene glycol compound was calculated by the Griffin method from the molecular weight of each fraction fractionated. Specifically, it was calculated by the above-mentioned equation (i).

(4) Ethylene urea Ethylene urea

(5) Water-soluble organic solvent glycerin (Gly)
Ethylene glycol (EG)

(6) pH adjuster urea

2. Preparation and Evaluation of Ink 2-1. Preparation and Evaluation of Ink Containing Reactive Dye (Examples 1 to 26, Comparative Examples 1 to 7)
The respective components were mixed to prepare the compositions as shown in Tables 2 to 4.

  Using the obtained ink, an image was formed by the ink jet printing method in the following procedure.

<Ink jet printing method>
(Ink application process)
The obtained ink was set in a line head type inkjet printing apparatus. Then, a solid image was formed on the cotton pretreated for the reactive dye using the obtained ink at main scanning 540 dpi × sub scanning 540 dpi. Here, dpi represents the number of ink droplets (dots) per 2.54 cm. The ejection frequency was 22 kHz.

(Coloring process)
The imaged fabric was steamed under conditions of relative humidity 100% and temperature 103 ° C. for 8 minutes to fix and develop the dye.

<Image evaluation>
Then, the surface density and back surface density of the obtained solid image and the rubbing test were conducted by the following method.

(Surface concentration, back surface concentration)
The surface concentration ^{L *} and the back surface concentration of the resulting solid image ^{L *,} was measured with a colorimeter CM-2022 measuring Minolta spectrometer. The higher the L ^* value, the lower the concentration, and the lower the L ^* value, the higher the concentration.

(Fabrication test)
The surface of the solid image of the printed matter on which the solid image was formed was scratched 10 times with a finger. Thereafter, the state of the solid image was visually observed and evaluated according to the following criteria.
○: No difference in color density is observed Δ: The color of the place where the fibers are misaligned (twisted) is light but the color remains ×: The color where the fibers are misplaced (twisted) Is white and almost no color remains

  Evaluation results of the inks of Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 2; evaluation results of Examples 9 to 17 and Comparative Examples 5 to 7 are shown in Table 3; evaluation results of Examples 18 to 26 Is shown in Table 4.

  As shown in Tables 2 to 4, for inks containing a first acetylene glycol surfactant and a second acetylene glycol surfactant, the difference between their HLB values is 4 or more and 7 or less In Examples 1 to 26 that were used, it is understood that color tone change due to fiber twisting can be suppressed in the rubbing test without lowering the surface concentration.

  In particular, it can be seen that, when the difference in HLB value is not too large, color tone change due to fiber twisting can be lessened in the rubbing test while maintaining the surface concentration (comparison of Examples 1 and 5).

  In addition, when the content mass ratio (W1: W2) of the first acetylene glycol surfactant to the second acetylene glycol surfactant is 6: 4 to 2: 8, the color tone change in the rubbing test is further increased. It can be seen that it can be reduced (contrast to Examples 9 and 14-17).

  In addition, it can be seen that the surface concentration is further increased by further adding urea as a pH adjuster (comparison of Examples 2 and 3, Comparison of Examples 6 and 7, and Comparison of Examples 10 and 11). It is considered that this is because the dyeability of the reactive dye is enhanced by adjusting the pH of the ink to a more appropriate range.

  Moreover, it turns out that the effect which can suppress the color tone change in a cloth ironing test becomes more remarkable by setting dye density | concentration to 20 mass% or more (contrast with Examples 18-21, Examples 23, 24, 26 and 27. Contrast). It is believed that this is because the higher the image density, the more noticeable the exposed side of the fiber not penetrated by the ink.

  On the other hand, in Comparative Example 1 using the ink in which the difference in HLB value is smaller than 4, the surface density is low, and it is understood that the color tone changes in the rubbing test. It is considered that this is because the HLB value of the second acetylene glycol surfactant is too low, the penetration of the ink is too fast, and the amount of ink remaining near the surface is small. On the other hand, in Comparative Examples 3 and 4 in which the ink having a difference in HLB value of more than 7 was used, the back surface density is low, and it is understood that color tone changes occur in the rubbing test. It is considered that this is because the penetration of the ink was too slow to penetrate into the inside of the fabric because the HLB value of the second acetylene glycol surfactant was too high. In Comparative Examples 2 and 6 in which the ink containing no ethylene urea was used, it is understood that color tone changes occur in the rubbing test. This is considered to be due to the fact that the surface tension of the ink did not rise sufficiently and it was difficult for the ink to penetrate to the inside of the cloth.

2-2. Preparation and Evaluation of Ink Containing Acid Dye (Examples 27 to 31, Comparative Examples 8 to 10)
Each component was mixed to prepare the composition as shown in Table 5, to prepare an ink.

  An image was formed in the same manner as in Example 1 except that the obtained ink was used, and a silk cloth pretreated for an acid dye was used as a fabric. Then, the surface density and back surface density of the obtained image and the rubbing test were conducted in the same manner as described above.

  The evaluation results of the inks of Examples 27 to 31 and Comparative Examples 8 to 10 are shown in Table 5.

  As shown in Table 5, an embodiment using an ink containing a first acetylene glycol surfactant and a second acetylene glycol surfactant and having a difference in HLB value of 4 or more and 7 or less In Examples 27 to 31, it is understood that color tone change due to fiber twisting can be suppressed in the rubbing test without lowering the surface concentration.

  On the other hand, in Comparative Example 8 using an ink in which the difference in HLB value is smaller than 4, the surface density is low, and it can be seen that color tone changes occur in the rubbing test. On the other hand, in Comparative Example 10 using an ink in which the difference in HLB value exceeds 7, the back surface density is low, and it can be seen that color tone changes occur in the rubbing test. In Comparative Example 9 in which an ink containing no ethylene urea was used, it was found that color tone changes occur in the rubbing test.

  ADVANTAGE OF THE INVENTION According to this invention, the inkjet textile printing ink which can suppress the color tone change by fiber twisting can be provided, without reducing surface concentration.

P fabric 2 transport means 21 adhesive belt 22 support roller 23 transport roller 24 nip roller 5 head carriage 6 hot air application means 6A fan 6B heating element

Claims (10)

A reactive dye or acid dye, a first acetylene glycol surfactant, a second acetylene glycol surfactant, ethylene urea, and water,
An inkjet textile printing ink satisfying the following formula (1), where h1 is the HLB value of the first acetylene glycol surfactant and h2 is the HLB value of the second acetylene glycol surfactant.
Formula (1): 4 ≦ h2-h1 ≦ 7   The inkjet textile printing ink according to claim 1, wherein the h1 is 6 or more and 12 or less, and the h2 is 10 or more and 19 or less.   The mass ratio of the first acetylene glycol surfactant to the second acetylene glycol surfactant is the same as the first acetylene glycol surfactant / the second acetylene glycol surfactant = The ink jet textile printing ink according to claim 1 or 2, which is 6/4 to 2/8.   The total content of the first acetylene glycol surfactant and the second acetylene glycol surfactant is 0.03% by mass or more and 2% by mass or less based on the total mass of the inkjet textile ink. The inkjet textile printing ink as described in any one of Claims 1-3.   The inkjet textile printing ink as described in any one of Claims 1-4 whose content of the said ethylene urea is 1 mass% or more and 15 mass% or less with respect to the total mass of the said inkjet textile printing ink.   The inkjet textile printing ink as described in any one of Claims 1-5 whose content of the said reactive dye is 20 mass% or more and 40 mass% or less with respect to the total mass of the said inkjet textile printing ink.   The inkjet textile printing ink as described in any one of Claims 1-5 whose content of the said acidic dye is 7 mass% or more and 15 mass% or less with respect to the total mass of the said inkjet textile printing ink.   The inkjet textile-printing method including the process of discharging the droplet of the inkjet textile printing ink as described in any one of Claims 1-7 from an inkjet recording head, and forming an image on a fabric.   The inkjet textile printing method according to claim 8, wherein the fabric comprises cellulose fiber or protein fiber.   The ink jet printing method according to claim 8, wherein the ink jet recording head is a line head.

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