JP2001115073A - Ink jet printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet printing ink capable of realizing nice images on fabrics through ink jet printing operation, and to provide a printing method using such an ink as described above. SOLUTION: This ink jet printing ink essentially comprises an acid dye, a surfactant, water and a compound of the formula given in the specification, being <=8.0 m.Pa.s (20 deg.C) in viscosity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION <Field of the Invention> The present invention relates to an ink containing an acid dye by an ink jet printing method, which is made from animal fibers such as silk and wool, polyamide fibers such as nylon or a blend containing at least one of these fibers. The present invention relates to an ink jet ink for printing on fibers and a method for printing and printing the same.

2. Description of the Related Art Ink jet printing methods include:
This is a printing method in which small droplets of ink are made to fly and adhere to a recording medium such as paper or transparency. This method
It has the feature that high-resolution, high-quality images can be printed at high speed with a relatively inexpensive device.

If this ink-jet printing method is applied to textile printing, excess ink generated in the conventional printing process, which can easily form various images on a fabric, is excellent in gradation and multicolor expression, etc. It has many advantages such as being effective for environmental protection.

The important points in ink-jet printing are that the ink can realize a printed image with high color development, that the ink can be adjusted to a viscosity range suitable for ink-jet printing, and that the ink has a favorable matching property with the pretreatment agent of the fabric and has good characteristics. The image can be realized, the ink drying time is relatively short, for example, no set-off occurs when the fabric is wound up after printing, and the ink can withstand long-term storage. It should be noted that the term “ink drying” as used in the present invention includes not only evaporation of ink components but also the fact that the ink penetrates the cloth and the transfer of the ink does not occur by touching with a finger or the like.

As ink-jet printing methods for printing by an ink-jet method using an ink composition using an acid dye, for example, JP-A-5-255627, JP-A-6-25576, JP-A-7-258982, and No. 9-296380.

[0006]

SUMMARY OF THE INVENTION The present inventor has recently developed an ink which is excellent in applicability to ink-jet printing and storage stability, and can realize a good image on a fabric by showing stable ejection performance, and an ink-jet using the ink. I found a printing method.

Accordingly, an object of the present invention is to provide an ink which is excellent in applicability and storage stability to an ink jet printing method and can realize a better image on a fabric, and an object of the printing method.

The ink for ink-jet printing according to the present invention is an ink-jet ink to be printed on a polyamide fiber cloth such as silk, wool, nylon, or the like, and the ink comprises at least an acid dye, a surfactant, water and the following formula: Contains the compound shown in (1) and has a viscosity of 8.0 mPa · s
(20 ° C.) or less.

[0009]

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Further, the ink-jet printing method of the present invention is a printing method in which the surface layer of the print head is subjected to an ink-repellent treatment and the ejection stability is excellent.

[0011]

DETAILED DESCRIPTION OF THE INVENTION <Inkjet printing ink> The acidic dye contained in the ink composition according to the present invention as a colorant includes an azo dye, an anthraquinone dye, a carbonium dye, a nitro dye, and a metal complex dye. Specific examples of such dyes include four basic colors of printing or C.I. I. Acid Yellow 1, 3, 7, 1
1, 17, 19, 23, 25, 29, 36, 38, 4
0, 42, 44, 49, 59, 61, 70, 72, 7
5, 76, 78, 79, 98, 99, 110, 111,
112, 114, 116, 118, 119, 127, 1
28, 131, 135, 141, 142, 161, 16
2,163,164,165,169,207,21
9, 246, C.I. I. Acid Red 1, 6, 8, 9,
13, 14, 18, 19, 24, 26, 27, 28, 3
2, 35, 37, 42, 51, 52, 57, 62, 7
5, 77, 80, 82, 83, 85, 87, 88, 8
9, 92, 94, 95, 97, 106, 111, 11
4, 115, 117, 118, 119, 129, 13
0, 131, 133, 134, 138, 143, 14
5, 149, 154, 155, 158, 168, 18
0, 183, 184, 186, 194, 198, 19
9, 209, 211, 215, 216, 217, 21
9, 249, 252, 254, 256, 257, 26
0, 262, 265, 266, 274, 276, 28
2,283,303,317,318,320,32
1, 322, 361, C.I. I. Acid Blue 1, 7,
9, 15, 22, 23, 25, 27, 29, 40, 4,
1, 43, 45, 49, 54, 59, 60, 62, 7
2, 74, 78, 80, 82, 83, 90, 92, 9
3, 100, 102, 103, 104, 112, 11
3, 117, 120, 126, 127, 129, 13
0, 131, 133, 138, 140, 142, 14
3,151,154,158,161,166,16
7, 168, 170, 171, 175, 182, 18
3, 184, 185, 187, 192, 199, 20
3, 204, 205, 225, 229, 234, 23
6, 300, C.I. I. Acid Black 1, 2, 7, 2
4, 26, 29, 31, 44, 48, 50, 51, 5
2, 58, 60, 62, 63, 64, 67, 72, 7
6, 77, 94, 107, 108, 109, 110, 1
12, 115, 118, 119, 121, 122, 13
1, 132, 139, 140, 155, 156, 15
7, 158, 159, 191, 234, and the like. In addition, any color other than the four basic colors such as orange, violet, green, and brown can be used as appropriate for expanding the color expression range of the printed image or for special colors. Specific examples of such dyes include C.I. I. Acid Orange 1,
7, 8, 10, 19, 20, 24, 28, 33, 41,
43, 45, 51, 56, 63, 64, 65, 67, 7
4, 80, 82, 85, 86, 87, 88, 95, 12
2, 123, 124, C.I. I. Acid Violet 7, 11, 15, 31, 34, 35, 41, 43, 4
7, 48, 49, 51, 54, 66, 68, 75, 7
8, 97, 106, C.I. I. Acid Green 3, 7,
9, 12, 16, 19, 20, 25, 27, 28, 3
5, 36, 40, 41, 43, 44, 48, 56, 5
7, 60, 61, 65, 73, 75, 76, 78, 7
9, C.I. I. Acid Brown 2, 4, 13, 14, 1
9, 20, 27, 28, 30, 31, 39, 44, 4
5, 46, 48, 53, 100, 101, 103, 10,
4, 106, 160, 161, 165, 188, 22
4, 225, 226, 231, 232, 236, 24
7, 256, 257, 266, 268, 276, 27
7, 282, 289, 294, 295, 296, 29
7, 299, 300, 301, 302 and the like. Further, these dyes can be used by appropriately mixing them to match a desired color. It is useful to add a complementary color to print a particularly good black color.

Further, when printing the ink of the present invention on a mixed fabric containing fibers which are difficult to dye with an acid dye, if another type of dye is added to the ink of the present invention and printing is performed, the mixed fabric can be further improved. A seal is obtained. For example, by performing ink-jet printing on a cloth made of silk and polyester with an ink containing a disperse dye added to the ink of the present invention, a good print quality can be obtained on polyester. Further, the acidic dye ink and the disperse dye ink may be ejected from separate inkjet print nozzles. The ejection order may be appropriately determined according to the printing system.

Further, a color which is difficult to express with an acid dye system can be expressed by blending another type of dye. For example, in the case of silk coated with the pretreatment agent of the present invention, wool, or a blend containing one of them, a wide range of colors including special colors can be expressed by adding a reactive dye to the ink of the present invention. It is possible. Further, the acidic dye ink and the reactive dye ink may be ejected from different nozzles. The ejection order may be appropriately determined according to the printing system.

In the ink of the present invention, the amount of the acid dye to be added may be appropriately determined.
It is preferably about 5% by weight, more preferably about 1 to 10% by weight. Further, the gradation of the printed material can be further improved by using a light and dark ink in which the dye density is changed to the same color or a similar color. In particular, this dark and light ink is effective for alleviating the graininess in the middle to low density region.

Further, the ink of the present invention is obtained by adding a surfactant. The ink containing the surfactant is advantageous in that it uniformly wets even on the pretreated fabric, reduces imprints, and penetrates into the fabric in a short time. In addition, the piezo-vibration type has the effect of improving bubble discharge in the print head, which causes ejection failure, and maintaining stable ejection.

Further, the printing ink according to the present invention contains an organic compound represented by the following formula (abbreviated as GEPOH).
GEPOH contained in the ink does not necessarily have to be a single compound. As long as the combination of l, m, and n is within the following range, various chemical structures may be mixed.

[0017]

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As an average value of GEPOH, l + m + n is 1
In this case, even if the print head is filled with ink and left for a long time, the ejection becomes stable immediately. On the other hand, if it is 30 or less, it is easy to adjust the viscosity range of the inkjet ink. A more preferred value is 2 or more, and an even more preferred value is 3 to 26. GEPOH can be formed by using glycerin as a starting material and adding a target molar amount of ethylene oxide or propylene oxide under an atmosphere such as an alkali. The addition state is polydispersed at the time of synthesis, but may be used as monodispersed through a process such as distillation for special applications. However, in an ink-jet ink system, the number of ethyleneoxy groups or propyleneoxy groups to be added preferably has a distribution from the viewpoint of improving clogging properties and printing quality. GEPOH may contain both an ethyleneoxy group and a propyleneoxy group in the same molecule, or may be a single adduct of both.

In the case of an ink-jet ink comprising an acidic dye, the viscosity may be lower than the appropriate viscosity range for ink-jet discharge depending on the kind of the dye. The GEPOH of the present invention has a thickener effect and is suitable for adjusting the ink to an appropriate viscosity range. Known thickeners include water-soluble polymers, which in this case have a significant adverse effect on dry clogging. On the other hand, the GEPOH of the present invention not only has a thickening effect as described above, but also has a humectant effect, and is also effective in improving clogging.

In particular, when the GEPOH of the present invention is combined with known humectants such as diethylene glycol, glycerin, and thiodiglycol, the desired viscosity of the ink can be adjusted with the desired amount of humectant.

Further, the GEPOH of the present invention is effective for reducing the amount of ink bubbles generated and for shortening the defoaming time. By suppressing bubbles, more stable inkjet discharge can be achieved. In particular, this effect becomes remarkable when the ink is ejected in a high temperature region exceeding 35 ° C. This ejection stabilizing effect is remarkable in combination with a nonionic activator or an alkylene glycol alkyl ether-added system.

The ink according to the present invention has a viscosity of 8.0 mPa · s or less at 20 ° C., preferably 1.5 to 6.0 mP.
a · s. If it is 8.0 mPa · s or less, ink can be ejected at normal environmental temperature without any problem. An ink exceeding 8.0 mPa · s at 20 ° C. has poor ejection stability in a low temperature region.

According to a preferred embodiment of the present invention, the dye is preferably purified to a concentration of 1% by weight or less as a salt derived from the dye in the ink composition. Utilization of such a purified dye is preferable because the ejection stability of the ink composition can be ensured at a high level, and the occurrence of rust on the metal part of the printer can be suppressed.

According to a preferred embodiment of the present ink, the surface tension of the ink is preferably 50 mN / m or less. More preferably, it is 40 to 25 mN / m. The surface tension can be adjusted by adding a surfactant to the ink component. Preferred surfactants are amphoteric, anionic and nonionic. Particularly, a nonionic acetylene glycol-based activator is preferable. The acetylene glycol-based surfactant improves the matching with the piezo-vibrator type ink jet head and maintains stable ejection.

In the ink of the present invention, it is preferable to use a polyhydric alcohol having a boiling point at normal pressure of 150 ° C. or higher as the organic solvent. Such an organic solvent can effectively prevent drying of the ink, and thereby has the effect of preventing nozzle clogging. Preferred examples include ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,
4-butanediol, 1,3-butanediol, 1,2
-Pentanediol, 1,5-pentanediol, 1,
2-hexanediol, 1,6-hexanediol,
1,2,6-hexanetriol, 1,8-octanediol, 1,2-octanediol, glycerin, mesoerythritol, pentaerythritol, thioglycol and the like. The amount of the polyhydric alcohol-based organic solvent having a boiling point of 150 ° C. or higher may be appropriately determined, but is preferably 50% by weight or less, more preferably 2 to 40% by weight, and still more preferably 2 to 20% by weight based on the ink. It is about weight. The amounts of these solvents are used alone or in combination in consideration of the dry clogging property of the print head and the storage stability of the ink.

The ink jet printing ink of the present invention preferably contains an alkylene glycol alkyl ether having a boiling point of 150 ° C. or higher. This solvent is effective not only for preventing the ink from drying out but also for stabilizing the ejection of the ink from the nozzles. This discharge stability effect is particularly effective for a discharge method using a piezoelectric vibrator. These materials include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, and the like. The addition amount of these alkylene glycol alkyl ethers may be appropriately determined,
It is preferably about 0.5 to 30% by weight, more preferably about 3 to 20% by weight, and still more preferably 5 to 30% by weight based on the ink.
It is about 15% by weight. These solvent amounts are used alone or in combination in consideration of the dry clogging property of the print head and the storage stability of the ink.

It is needless to say that it is preferable that the liquid organic components constituting the ink have substantially mutual compatibility. Here, “substantially compatible” means that the obtained ink has a solubility that does not cause phase separation and does not cause precipitation. More preferably,
It means a degree of compatibility that does not cause phase separation between liquid components at room temperature even when water in the ink evaporates. An ink having substantial compatibility ejects ink jet more stably.

Further, in the ink of the present invention, it is preferable to add a urea-based substance. Preferred examples of these include urea,
Examples thereof include alkyl ureas such as dimethyl urea, monomethyl thiourea, thiourea, and dimethyl thiourea, and alkyl thioureas. According to an embodiment of the present invention, they have both the effect of preventing dry clogging of the ink and the effect of a hydrotropic agent.
2 to 10% by weight of urea or alkyl urea in solid content
And thiourea in an amount of 1 to 5% by weight in combination. The addition of these to the ink is effective not only for the effect of long-term dry clogging but also for improving the printing density. In addition, thiourea is particularly effective for improving leveling properties. Also, if this urea-based substance is added to the ink liquid, the amount of the urea-based additive required for the fabric pretreatment agent can be reduced or eliminated. This is extremely effective for preserving the environment.

Further, the surfactant to be added to the ink jet printing ink of the present invention is preferably a nonionic surfactant. With this surfactant, an ink having more excellent ejection stability can be obtained. The amount of the nonionic surfactant added may be appropriately determined, but may be 0.05 to 100% with respect to the ink composition.
It is preferably about 5% by weight, more preferably about 0.1 to 3% by weight. When this surfactant is combined with an alkylene glycol alkyl ether, a pyrrolidone-based solvent, or thioglycol, ejection stability can be selected in a wide temperature range. This effect is remarkably exhibited in an ink jet system using a piezoelectric vibrator.

Preferred examples of the nonionic surfactant include an ethylene glycol surfactant, a polyhydric alcohol surfactant, and an acetylene glycol surfactant. According to a preferred embodiment of the present invention, the use of an acetylene glycol-based surfactant is preferred. Activators of this type include, for example, Olphin Y, Surfynol 82,
Surfynol 440, Surfinol 465, Surfinol 485 (all manufactured by Air Produc
ts and Chemicals. Inc. ).

According to a preferred embodiment of the present invention, the nonionic surfactant has a boiling point of 15%.
Solubility in organic solvent of 0 ° C or higher is 10 g / 100 g
It is preferable to use the above. The use of a nonionic surfactant and an organic solvent satisfying such a relationship has an effect of easily securing the ejection stability from the nozzle even under a high temperature environment. This effect is particularly effective for a piezo oscillator type ink jet printing system. Also,
In a piezo oscillator type ink-jet system, the addition of a nonionic surfactant, preferably an acetylene glycol-based surfactant, stabilizes the ink ejection amount for each dot and makes it easier to reproduce the printing density.

A nonionic surfactant is effective for improving leveling properties and preventing bleeding. Ink jet printing inks, which have a significantly lower viscosity than conventional printing pastes used for silk screens and the like, are liable to cause a drawback that ink flow occurs on the printing cloth and it is difficult to obtain levelness. This phenomenon is particularly likely to occur in solid areas. In addition, this ink flow tends to cause bleeding at the color boundary. The nonionic surfactant of the present invention is effective in preventing these disadvantages. In particular, an acetylene glycol-based surfactant is effective for uniform wetting to a pretreated cloth, excellent osmosis, and prevention of mottling and bleeding.

Incidentally, the solid in the present invention means a state where an area of 5 * 5 mm or more is printed without gaps.

The preferred pH of the printing ink of the present invention is 5.0.
１11.0. More preferably, it is 7.0 to 9.5. If the pH is too low, corrosion of the metal parts of the printer tends to progress, which may hinder long-term use. If the pH is more than 11, damage may be caused depending on the type of fabric.

Further, it is desirable to add a sequestering agent to the ink jet printing ink of the present invention. A preferable addition amount is 0.001 to 0.1% by weight, and more preferably, 0.1 to 0.1% by weight.
005 to 0.03% by weight. The blocking agent has an effect of stably discharging the inkjet ink of the present invention for a long period of time. Further, a stable density and hue can be secured on the printing cloth. As the metal sequestering agent, ethylenediaminetetraacetic acid (EDTA), EDTA salt, hydroxyethylethylenediaminetriacetic acid (EDTA-OH) and the like are preferable.

In the ink jet printing ink according to the present invention, water is the main solvent. As the water, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, or distilled water, or ultrapure water can be used. In addition, it is preferable to use water sterilized by ultraviolet irradiation or addition of hydrogen peroxide, since mold and bacteria can be prevented from occurring when the ink is stored for a long period of time.

The inkjet printing ink of the present invention may contain additives in addition to the above-mentioned components to improve various properties of the ink. Examples of such additives include preservatives. Preferred examples of preservatives include Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, Proxel TN, and the like.

The ink jet textile printing ink of the present invention has a close relationship between the solubility of the constituent acidic dyes and the ink ejection stability. When the dye concentration is relatively high, the ejection stability is improved by adding a pyrrolidone solvent. As these solvents, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1.3-dimethylimidazolidinone and the like are preferable.
When these solvents are used in combination with an acetylene glycol-based surfactant, the ejection stability is further improved, and this effect is remarkably exhibited in a piezo oscillation type ejection system.

<Inkjet printing method> Further, in the ink jet printing method according to the present invention, the ejected ink droplets are adhered to a fiber mainly containing animal protein such as silk or wool, or a cloth made of polyamide fiber such as nylon. An inkjet printing method comprising:
It is made using the ink according to the present invention described above.

The fabric is preferably pre-treated. The pretreatment agent preferably contains a paste, and preferably, natural gums such as guar and locust bean, starches, sodium alginate, seaweeds such as seaweed, plant skins such as pectic acid, methylcellulose, Cellulose derivatives such as ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, roasted starch, alpha starch, carboxymethyl starch, carboxyethyl starch, processed starch such as hydroxyethyl starch, processed natural gums such as shiratsu gum, roast bean gum etc. , Algin derivatives, synthetic pastes such as polyvinyl alcohol and polyacrylate, emulsions and the like are used. In particular, a paste having poor dyeing properties with the dye to be used is preferably used.

Further, as a cloth pretreatment agent compatible with the ink of the present invention, it is preferable to add a hydrotroping agent to the paste. Examples of the hydrotrope include alkyl ureas such as urea, dimethyl urea, thiourea, monomethyl thiourea, and dimethyl thiourea. The printing density can be further improved by adding a hydrotropic agent. The amount of these hydrotropic agents can be reduced by adding urea, a combination of alkyl urea and thiourea.
The hydrotrope is effective in improving the stability after pretreatment formulation and stabilizing the surface state of the padding cloth. In addition, thiourea is particularly effective for improving leveling properties. The hydrotrope is determined by matching with the ink, but 15% o. w.
p or less is fine. When the hydrotroping agent has already been added to the inkjet ink, the amount of the hydrotroping agent as the pretreatment agent can be reduced to no addition, which is an effective printing method for environmental protection.

Further, as a cloth pretreatment agent suitable for the ink of the present invention, it is preferable to use an acid ammonium salt such as ammonium sulfate, ammonium tartrate, or sodium diphosphate as a pH adjuster. The amount of these additives varies depending on the type of dye, but is 0.2 to 5% o.
w. p, preferably 0.5-3% o. w. p. By adding these pH adjusters, hue stabilization and improvement in dyeing properties can be achieved.

The application of the pretreatment agent may be carried out according to a conventional method, for example, a padding method. The mangle pressure, speed, drying time and the like at that time may be determined as appropriate. The padding reduction ratio is preferably 40% or more, and more preferably 60% or more. Increasing the aperture ratio is effective in improving the fixing density.

The amount of the pretreatment agent attached is not particularly problematic at most, but is preferably 25 g / m 2 or less from the viewpoint of environmental friendliness. Specifically, 3 to 25 g / m2, preferably 5 to
20 g / m2, more preferably 7 to 15 g / m2. When the amount of adhesion is increased, the fixability of the ink jet printing ink is improved, and the printing density is increased. Also,
Even if the amount exceeds 25 g / sq.m., There is no hindrance to the print, but the print density enters the saturated region.

The fabric which can be used for ink-jet printing according to the present invention comprises a pretreated animal fiber such as silk or wool, a fabric composed of amide fibers, or a blend containing at least one of these fibers.

The ink-jet printing method according to the present invention includes a so-called piezo head type in which ink droplets are formed and ejected by mechanical volume change of a piezoelectric element. Any of a so-called bubble jet or thermal jet type in which droplets are formed and ejected may be used.

The preferred recording method of the present invention is an ink-jet printing method using a piezoelectric element. The piezo type is extremely excellent in durability and is most suitable for the field requiring stable ejection for a long time as in the present invention. In addition, the ink of the present invention is particularly excellent in matching with a piezo-type print head, and achieves stable continuous ejection for a long time in a wide temperature range. This is suitable for the field of ink-jet printing of a long object requiring enormous ejection.

When the ink of the present invention is filled in a piezo-vibrator type ink jet print head and ejected, it is desirable that the surface of the nozzle plate of the print head is subjected to an ink repellent treatment. Applying the ink-repellent treatment makes it difficult for the ink to bend in flight and prints an image with excellent reproducibility on a desired cloth.

It is preferable that the ink repellent treatment is also applied to the inner surface of the nozzle hole. By applying the ink to the inner surface, the ink meniscus position is stabilized, and the ejection stability is further improved. In addition, it is difficult for ink to come out on the nozzle plate surface, and the ink repellency of the nozzle surface can be maintained for a longer time.

The nozzle plate is drilled with a desired diameter. Constituent materials include metals, ceramics, silicon,
Made of glass, plastic, etc., preferably titanium,
Single material such as chromium, iron, cobalt, nickel, copper, zinc, tin, gold, etc. or alloys such as nickel-phosphorus alloy, tin-copper-phosphorus alloy, copper-zinc alloy, stainless steel, polycarbonate, polysulfone, acrylic nitrile -Butadiene-styrene copolymer, polyethylene terephthalate,
It is desirable to be formed of polysulfone and various photosensitive resins.

The method for treating the surface of these materials with ink is not particularly limited. For example, the material is immersed in an electrolytic solution in which nickel ions and water-repellent polymer resin particles are dispersed by electric charges, and immersed while stirring the solution. The preferred method is to perform eutectoid plating on the surface of the nozzle plate. As a water-repellent polymer resin material used for this eutectoid plating, a resin such as polytetrafluoroethylene, polyperfluoroalkoxybutadiene, polyvinylidene, polyfluorovinyl, polydiperfluoroalkyl fumarate or the like is used alone or in combination. It is preferred to use. Further, the metal material does not need to be limited to nickel, and for example, copper, silver, tin, zinc and the like can be appropriately selected. Preferably, nickel, a nickel-cobalt alloy, a nickel-boron alloy or the like having a large surface hardness and excellent abrasion resistance are preferred.

According to a preferred aspect of the present invention, it is desirable that the ink ejection amount is 120 dots / inch or more and the ink ejection amount in solid printing is 5 g / m 2 or more. If the ejection density is 120 dots / inch or more, the printed material is less grainy. Further, if the dark and light inks are used in combination, a better printed image can be achieved. When the ink ejection amount exceeds 5 g / m2, it is easy to express high density printing.

The cloth to which the ink composition has been attached is subjected to post-treatment and fixed to the fibers. Further, it is preferable that the unfixed colorant and other ink compositions are sufficiently removed by the washing step. According to a preferred embodiment of the present invention, the post-treatment is divided into several steps. First, after the ink composition is adhered to the fabric, the fabric is cooled to a room temperature to 120 ° C.
It is preferable to leave the ink for 0.5 to 30 minutes to pre-dry the ink. This preliminary drying is effective for improving the printing density and preventing bleeding. In addition, this preliminary drying includes that the ink permeates into the fabric.

According to a preferred embodiment of the present invention, it is further preferable that the preliminary drying is performed by heating in a continuous step. The fabric is supplied in a roll form to an ink jet printing machine for printing, and is subjected to a drying process before winding the printed fabric. The dryer can be directly connected to the printing machine or it can be away. In the dryer, the treatment is preferably performed at 150 ° C. or lower for 0.5 to 30 minutes. The drying method is preferably an air convection method, a heating roll direct attachment method, an irradiation method, or the like.

Further, it is preferable that the pre-dried fabric is further fixed by steaming. Preferred conditions are humidity 5
0-100% (more preferably humidity 80-100%) and temperature 90-120 ° C (preferably 95-105 ° C)
And fixing for 5 to 120 minutes (preferably 20 to 60 minutes). Further, after fixing, it is preferable to wash with warm water containing at least a nonionic surfactant. The printing cloth post-processed based on such a process has excellent coloring and reduced ink bleeding.

It is preferable to change the conditions of the fixing step in the post-processing step depending on the type of the cloth. In particular,
It is preferable to change the time. For example, if the fabric is wool, the time is 20-120 minutes, preferably 30 minutes.
About 90 minutes is preferable. When the cloth is silk, the time is preferably 5 to 40 minutes, and more preferably about 15 to 30 minutes. When the fabric is nylon, it is 5 to 90 minutes, preferably 10 to 90 minutes.
About 60 minutes is preferable.

[0057]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Preparation of Ink Composition> Ink 1
Was adjusted in the following procedure. 4 into 110cc sample bottle
A 10% by weight aqueous solution of Surfynol 465 was added to 52 g of water at 0 ° C. while stirring with a magnetic stirrer.
g, preservative Proxel XL 10% by weight aqueous solution
g and a 1% by weight aqueous solution of the chelating agent EPDA 0.5
g was added. Further, 10 g of Liponic EG-1 and 7 g of Acid Yellow 49 were added, and the mixture was stirred with heating with a magnetic stirrer until the dye was dissolved. Further, 10 g of diethylene glycol, 8 g of glycerin and 5 g of diethylene glycol mono-n-butyl ether were added. After the addition, the mixture was stirred with a magnetic stirrer for 10 minutes to obtain an ink.

<Ink 1> C.I. I. Acid Yellow 49.7% by weight GEPOH (Liponic EG-1) 10% by weight Diethylene glycol 10% by weight Glycerin 8% by weight Diethylene glycol mono-n-butyl ether 5% by weight Surfinol 465 0.5% by weight Proxel XL 0.25% by weight EPDA 0 0.005% by weight Water Remaining In addition, 100 grams of inks 2 to 7 having the following compositions were prepared.

<Ink 2> C.I. I. Acid Red 52 7% by weight GEPOH (Liponic EG-7) 7% by weight Diethylene glycol 7% by weight Triethylene glycol mono-n-butyl ether 3% by weight Surfinol 465 0.7% by weight N-methyl-2-pyrrolidone 5% by weight Preservative Agent 0.2% by weight Chelating agent 0.01% by weight Water remaining amount <Ink 3> I. Acid Blue 140 10% by weight GEPOH (l + m + n = 3) (adduct is ethyleneoxy group) 5% by weight 2-Pyrrolidone 5% by weight Surfinol 465 0.9% by weight Preservative 0.15% by weight Chelating agent 0.015% by weight % Water Remaining <Ink 4> I. Acid Black 52 7% by weight GEPOH (l + m + n = 7) (the adduct is an ethyleneoxy group) 8% by weight Diethylene glycol 5% by weight Thiodiglycol 3% by weight Surfinol 485 1.1% by weight Preservative 0.1% by weight Chelating agent 0.02% by weight Water remaining amount <Ink 5> Acid Yellow 1 16% by weight GEPOH (l + m + n = 3) (addition product is propyleneoxy group) 15% by weight Thiodiglycol 10% by weight Anionic activator 0.5% by weight Preservative 0.05% by weight Chelating agent 0.025% by weight Water remaining amount <Ink 6> I. Acid Red 26 8% by weight GEPOH (Liponic EG-7) 7% by weight Triethylene glycol mono-n-butyl ether 3% by weight Urea 7% by weight Surfynol 465 0.7% by weight Preservative 0.2% by weight Chelating agent 0. 01% by weight Water Remaining <Ink 7> I. 138 8% by weight GEPOH (Liponic EG-7) 10% by weight Surfynol 465 0.7% by weight Preservative 0.2% by weight Chelating agent 0.01% by weight Water remaining amount <Ink 8> I. Black 155 8% by weight GEPOH (l + m + n = 10) (additive is ethyleneoxy group) 10% by weight Surfinol 465 0.7% by weight Preservative 0.2% by weight Chelating agent 0.01% by weight Water remaining amount Liponic Is Lipo Chemicals In
c and is commercially available.

<Pretreatment agent for cloth> While slowly stirring 1 liter of water, 15 g of a starch-based paste was added over about 4 hours. With further stirring, 1.0 g of urea and 0.1 g of thiourea were added.
5 grams were added. Leave for one day, make sure that there is no wandering, and 25% ammonium tartrate 5% o. w. p was added and the mixture was further stirred for 1 hour to prepare a pretreatment agent 1.

A pretreatment agent 2 was obtained in the same manner as above except that urea was changed to dimethyl urea and thiourea was changed to dimethyl thiourea.

<Padding> The padding of the pretreatment agent is as follows:
The test was performed at room temperature using HVF350 manufactured by Mathis. Specifically, the silk cut in advance into 210 × 315 mm is pressure 2b.
The padding was carried out under the following conditions: ar, speed: 3 m / min, drawing ratio: 80%.

<Inkjet Printing> A modified inkjet printer MJ930C (manufactured by Seiko Epson Corporation) was filled with ink and printed on the pretreatment agent described above. Nickel on the nozzle plate and part of the nozzle hole
Ink repellent treatment by Teflon eutectoid plating was also used.

<Post-treatment> A fixing operation was carried out using a steamer-DHe type manufactured by Mathis. The steaming was performed for 30 minutes in an environment of a temperature of 102 ° C. and a humidity of 98% or more.
Thereafter, washing was performed. First, as a first cleaning, a nonwoven activator (1.5 g / l) and sodium carbonate (1 g)
/ L) at room temperature. The immersion time was 10 minutes with occasional stirring. The bath ratio was 1/50. The removal of the printing cloth was squeezed lightly and the second cleaning was started. The pre-washed cloth was immersed in a 50 ° C. aqueous solution of a nonionic activator (1.5 g / l) and sodium carbonate (1 g / l). The immersion time was 15 minutes with occasional stirring. The bath ratio was 1/50. The sufficiently washed cloth was air-dried and ironed.

<Evaluation Test 1> Printing was performed using the ink and the pretreatment agent in the combinations shown in the following tables. The OD value of the printed portion of the obtained printed fabric was measured. The results are shown below.

Ink composition Pretreatment agent OD value ―――――――――――――――――――――― Ink 8 Pretreatment agent 1.41 Ink 8 Pretreatment agent 2 43 ――――――――――――――――――――――――

<Evaluation Test 2> Immediately after the preparation of the ink composition, printing was performed according to the above to obtain a printed cloth. On the other hand, after the ink composition was prepared, it was allowed to stand at a temperature of 50 ° C. for one week, and thereafter, printing was performed according to the above to obtain a printed cloth.

OD of printed portion of printed cloth before and after standing
The value was measured. The results were as shown in the following table. In addition, the above-mentioned pretreatment agent 2 was used as a pretreatment agent in all cases. Ink composition OD value before leaving OD value after leaving ―――――――――――――――――――――――――― Ink 1 1.35 1.35 Ink 2 1 .39 1.38 Ink 3 1.47 1.47 Ink 4 1.40 1.40 Ink 5 1.34 1.34 Ink 6 1.40 1.39 Ink 7 1.39 1.39 Ink 8 1.43 1.42 ――――――――――――――――――――――――――――

<Evaluation Test 3> Immediately after the ink composition was prepared, printing was performed in accordance with the above to obtain a printed cloth. On the other hand, after the ink composition was prepared, it was allowed to stand at a temperature of 60 ° C. for one week, and thereafter, printing was performed according to the above to obtain a printed fabric. The OD value of the printed portion of the printed cloth before and after standing was measured. The results were as shown in the following table.

The above pretreatment agent 2 was used as a pretreatment agent in all cases. Ink composition OD value before standing OD value after standing ―――――――――――――――――――――――――――― Ink 1 1.35 1.33 Ink 2 1.39 1.38 Ink 3 1.47 1.46 Ink 4 1.40 1.39 Ink 5 1.34 1.34 Ink 6 1.40 1.39 Ink 7 1.39 1.38 Ink 8 1 .43 1.42 ――――――――――――――――――――――――――――――

<Evaluation Test 4> Inkjet Printer M
J930C was filled with Ink 1 and printed. It was confirmed that ink droplets were ejected from all nozzles of the recording head and that there was no flight bending. After the printer was left at 40 ° C. for 7 days, printing was performed. All nozzles fired without the cleaning operation provided in the printer. There was no flight bend.

<Evaluation Test 5> An ink jet printer MJ930C equipped with a head not subjected to the ink-repellent treatment was filled with inks 1-4 and printed. It was confirmed that ink droplets were ejected from all nozzles of the recording head and that there was no flight bending. The printer was left at 40 ° C. for 7 days before printing. All nozzles fired without cleaning, but there was a flight bend of about 4%. After printing on the fabric treated with the pre-treatment agent 1, predetermined fixing and washing were performed to check the print quality. However, flight bending was not visually observed and a high-quality printed image was secured.

Further, by cleaning the print head once, the flight bending was eliminated. Then 100 on A4 paper
I printed it, but there was no problem.

<Evaluation Test 6> The inks 1 to 4 were filled in an ink jet printer MJ930C,
Printing was performed on 20,000 A4 recording papers at 0 ° C. and 40 ° C. All nozzles ejected at any temperature. No flight bends occurred.

<Evaluation Test 7> Ink 5 to 8 were used for evaluation test 4.
The nozzle plate of the printer used in the above was filled into an ink jet printer MJ930C without ink-repellent treatment, and A4 recording paper 2 was set at ambient temperatures of 0 ° C, 20 ° C, and 40 ° C.
Printing was performed on 0000 sheets. All nozzles ejected at any temperature. In the 40 ° C. test, several nozzles were bent after ejecting about 3000 sheets.

When the pre-treated cloth was printed and fixed with the head, no flight bending was observed. Slight ink bleeding during steaming eliminated the flight bend.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) D06P 3/82 D06P 5/00 111A 5/00 111 B41J 3/04 101Y F-term (reference) 2C056 FC01 2H086 BA22 BA53 BA57 BA59 BA60 BA61 4H057 AA02 BA02 CA12 CA29 CB25 CC02 DA01 DA21 DA22 GA06 HA03 4J039 AE07 BC07 BC09 BC13 BC37 BC54 BE04 BE12 BE15 BE22 BE32 EA41 EA42 EA44 FA03 GA24

Claims (15)

[Claims] 1. A composition containing at least an acid dye, a surfactant, water and a compound represented by the following formula (1), and having a viscosity of 8.0 mP.
An ink jet textile printing ink having an a · s (20 ° C.) or less. Embedded image 2. The ink jet printing ink according to claim 1, wherein the salt as an impurity derived from the dye is 1% by weight or less. 3. The ink jet textile printing ink according to claim 1, which has a surface tension of 50 mN / m or less. 4. The ink jet textile printing ink according to claim 1, comprising a polyhydric alcohol having a boiling point of 150 ° C. or higher. 5. The ink jet textile printing ink according to claim 1, comprising an alkylene glycol alkyl ether having a boiling point of 150 ° C. or higher. 6. The ink jet printing ink according to claim 1, which comprises at least one of urea, thiourea, alkyl-substituted urea, and alkylthiourea-based compound. 7. The ink jet printing ink according to claim 1, wherein the surfactant is an acetylene glycol derivative. 8. The ink jet printing ink according to claim 1, further comprising a metal sequestering agent. 9. An ink-jet printing method in which the ink-jet printing ink according to claim 1 is filled into an ink-jet print head using a piezo vibrator to perform ink-jet printing. 10. An ink-jet printing method in which the ink-jet printing ink according to claim 1 is filled into a piezo-vibrator type ink-jet print head having a nozzle surface provided with an ink-repellent film layer and printed. 11. The ink-jet printing method according to claim 10, wherein a part of the ink-repellent film is inserted into the inner surface of the nozzle. 12. The ink jet printing method according to claim 10, wherein the ink repellent film layer is formed by eutectoid plating. 13. An ink jetting method according to claim 1, wherein the ink jet textile printing ink has an ink jet density of 120 dots / inch or more and the solid ink has an ink jet amount of 5 g / sq. Claim 10 using:
13. The ink-jet printing method according to any one of items 12 to 12. 14. An ink-jet printing method for printing on a fabric using the ink-jet printing ink according to any one of claims 1 to 8, wherein the fabric contains at least a pH adjusting acid as a pretreatment agent. Characteristic inkjet printing method. 15. A fabric printed by the inkjet printing method according to claim 10. Description: